A method for producing an optically active, fluorine-containing, carbonyl-ene product represented by formula wherein Rf represents a trifluoromethyl group, R represents a methyl group or ethyl group, each of R 1, R 2, R 3, R 4 and R 5 independently represents a hydrogen atom, alkyl group, substituted alkyl group, aromatic ring group, or substituted aromatic ring group, * represents an asymmetric carbon, but is not an asymmetric carbon in case that R 4 and R 5 are the same substituents, and wave line represents an E configuration or Z configuration in geometrical configuration of the double bond, the method comprising reacting a fluorine-containing α-ketoester represented by formula wherein Rf and R respectively represent the same substituents as above, with an alkene represented by formula wherein each of R 1, R 2, R 3, R 4 and R 5 independently represents the same substituent as above, in the presence of a bivalent cationic transition metal complex having an optically active ligand, wherein the bivalent cationic transition metal complex is represented by the general formula, wherein, in the general formula, Y represents Ni, Pd, Pt or Cu, Z represents SbF 6, ClO 4 BF 4, OTf (Tf represents CF 3 SO 2), AsF 6, PF 6, or B(3,5-(CF 3) 2 C 6 H 3) 4], and X-*-X represents (a) an optically active SEGPHOS derivative represented by the following formula, wherein R represents C 6 H 5, 3,5-(CH 3) 2 C 6 H 3, or 4-CH 3 O-3,5-(t-C 4 H 9) 2 C 6 H 2, (b) an optically active BINAP derivative represented by the following formula, wherein R represents C 6 H 5, 4-CH 3 C 6 H 4, or 3,5-(CH 3) 2 C 6 H 3, (c) an optically active BIPHEP derivative represented by the following formula, wherein R represents H, CH 3, or CH 3 O, (d) an optically active P-Phos derivative represented by the following formula, wherein R represents C 6 H 5, 4-CH 3 C 6 H 4, or 3,5-(CH 3) 2 C 6 H 3, (e) an optically active PhanePhos derivative represented by the following formula, wherein R represents C 6 H 5, 4-CH 3 C 6 H 4, or 3,5-(CH 3) 2 C 6 H 3, (f) an optically active l,4-Et 2 -cyclo-C 6 H 8 -NUPHOS represented by the following formula, or (g) an optically active BOX derivative represented by the following formula, wherein R represents i-C 3 H 7, t-C 4 H 9, or C 6 H 5, characterized in that the reaction is performed in the absence of reaction solvent, and wherein usage of the bivalent cationic transition metal complex having the optically active ligand is 0.001 moles or less relative to 1 mole of the fluorine-containing α-ketoester represented by formula. wherein Rf represents a trifluoromethyl group, R represents a methyl group or ethyl group, each of R 1, R 2, R 3, R 4 and R 5 independently represents a hydrogen atom, alkyl group, substituted alkyl group, aromatic ring group, or substituted aromatic ring group, * represents an asymmetric carbon, but is not an asymmetric carbon in case that R 4 and R 5 are the same substituents, and wave line represents an E configuration or Z configuration in geometrical configuration of the double bond, the method comprising reacting a fluorine-containing α-ketoester represented by formula wherein Rf and R respectively represent the same substituents as above, with an alkene represented by formula wherein each of R 1, R 2, R 3, R 4 and R 5 independently represents the same substituent as above, in the presence of a bivalent cationic transition metal complex having an optically active ligand, wherein the bivalent cationic transition metal complex is represented by the general formula, wherein, in the general formula, Y represents Ni, Pd, Pt or Cu, Z represents SbF 6, ClO 4 BF 4, OTf (Tf represents CF 3 SO 2), AsF 6, PF 6, or B(3,5-(CF 3) 2 C 6 H 3) 4], and X-*-X represents (a) an optically active SEGPHOS derivative represented by the following formula, wherein R represents C 6 H 5, 3,5-(CH 3) 2 C 6 H 3, or 4-CH 3 O-3,5-(t-C 4 H 9) 2 C 6 H 2, (b) an optically active BINAP derivative represented by the following formula, wherein R represents C 6 H 5, 4-CH 3 C 6 H 4, or 3,5-(CH 3) 2 C 6 H 3, (c) an optically active BIPHEP derivative represented by the following formula, wherein R represents H, CH 3, or CH 3 O, (d) an optically active P-Phos derivative represented by the following formula, wherein R represents C 6 H 5, 4-CH 3 C 6 H 4, or 3,5-(CH 3) 2 C 6 H 3, (e) an optically active PhanePhos derivative represented by the following formula, wherein R represents C 6 H 5, 4-CH 3 C 6 H 4, or 3,5-(CH 3) 2 C 6 H 3, (f) an optically active l,4-Et 2 -cyclo-C 6 H 8 -NUPHOS represented by the following formula, or (g) an optically active BOX derivative represented by the following formula, wherein R represents i-C 3 H 7, t-C 4 H 9, or C 6 H 5, characterized in that the reaction is performed in the absence of reaction solvent, and wherein usage of the bivalent cationic transition metal complex having the optically active ligand is 0.001 moles or less relative to 1 mole of the fluorine-containing α-ketoester represented by formula.