Process for hydrocyanation of terminal alkynes wherein a terminal alkyne is reacted with a -CN source selected from HCN and/or cyanohydrine in the presence of a Rh-complex and in the presence of a solvent in a temperature range of 70°C to 130°C whereby an E-alkenyl nitrile is obtained: wherein R is i) a straight chain, branched chain or cyclic aliphatic C 1 to C 20 hydrocarbon, optionally having one or more unsaturated bonds, C 3 -C 8 -heterocycloalkyl, C 6 to C 20 aryl, (C 1 -C 6)-alkyl-C 6 to C 20 -aryl, (C 1 -C 6)-alkyl-C 5 to C 20 -heteroaryl, each hydrocarbon optionally being substituted by one or more groups selected from C 1 to C 20 straight chain, branched chain or cyclic aliphatic hydrocarbons, optionally having one or more unsaturated bonds, C 3 -C 8 -heterocycloalkyl, C 6 to C 20 aryl, (C 1 -C 6)-alkyl-C 6 to C 20 -aryl, (C 1 -C 6)-alkyl-C 5 to C 20 -heteroaryl or heterosubstituents; or ii) -SiR I R II R III, wherein R I, R II and R III may be same or different and each stands for a straight chain, branched chain or cyclic aliphatic C 1 to C 20 hydrocarbon, optionally having one or more unsaturated bonds, C 3 -C 8 -heterocycloalkyl, C 6 to C 20 aryl, (C 1 -C 6)-alkyl-C 6 to C 20 -aryl, C 5 to C 20 -heteroaryl, (C 1 -C 6)-alkyl-C 5 to C 20 -heteroaryl, each hydrocarbon optionally being substituted by one or more groups selected from C 1 to C 20 straight chain, branched chain or cyclic aliphatic hydrocarbons, optionally having one or more unsaturated bonds, C 3 -C 8 -heterocycloalkyl, C 6 to C 20 aryl, (C 1 -C 6)-alkyl-C 6 to C 20 -aryl, (C 1 -C 6)-alkyl-Cs to C 20 -heteroaryl or heterosubstituents; wherein R 1 and R 2 may be same or different and each stands for a straight chain, branched chain or cyclic aliphatic C 1 to C 20 hydrocarbon, optionally having one or more unsaturated bonds, C 3 -C 8 -heterocycloalkyl, C 6 to C 20 aryl, (C 1 -C 6)-alkyl-C 6 to C 20 -aryl, (C 1 -C 6)-alkyl-C 5 to C 20 -heteroaryl, each hydrocarbon optionally being substituted by one or more groups selected from C 1 to C 20 straight chain, branched chain or cyclic aliphatic hydrocarbons, optionally having one or more unsaturated bonds, C 3 -C 8 -heterocycloalkyl, C 6 to C 20 aryl, (C 1 -C 6)-alkyl-C 6 to C 20 -aryl, (C 1 -C 6)-alkyl-Cs to C 20 -heteroaryl or heterosubstituents; wherein cat Rh I stands for a Tp-Rhodium complex with a mono- or bidentate phosphine, wherein Tp stands for (tris(1-pyrazolyl)borohydride, and wherein solvent stands for an organic solvent, preferably a aprotic polar organic solvent. wherein R is i) a straight chain, branched chain or cyclic aliphatic C 1 to C 20 hydrocarbon, optionally having one or more unsaturated bonds, C 3 -C 8 -heterocycloalkyl, C 6 to C 20 aryl, (C 1 -C 6)-alkyl-C 6 to C 20 -aryl, (C 1 -C 6)-alkyl-C 5 to C 20 -heteroaryl, each hydrocarbon optionally being substituted by one or more groups selected from C 1 to C 20 straight chain, branched chain or cyclic aliphatic hydrocarbons, optionally having one or more unsaturated bonds, C 3 -C 8 -heterocycloalkyl, C 6 to C 20 aryl, (C 1 -C 6)-alkyl-C 6 to C 20 -aryl, (C 1 -C 6)-alkyl-C 5 to C 20 -heteroaryl or heterosubstituents; or ii) -SiR I R II R III, wherein R I, R II and R III may be same or different and each stands for a straight chain, branched chain or cyclic aliphatic C 1 to C 20 hydrocarbon, optionally having one or more unsaturated bonds, C 3 -C 8 -heterocycloalkyl, C 6 to C 20 aryl, (C 1 -C 6)-alkyl-C 6 to C 20 -aryl, C 5 to C 20 -heteroaryl, (C 1 -C 6)-alkyl-C 5 to C 20 -heteroaryl, each hydrocarbon optionally being substituted by one or more groups selected from C 1 to C 20 straight chain, branched chain or cyclic aliphatic hydrocarbons, optionally having one or more unsaturated bonds, C 3 -C 8 -heterocycloalkyl, C 6 to C 20 aryl, (C 1 -C 6)-alkyl-C 6 to C 20 -aryl, (C 1 -C 6)-alkyl-Cs to C 20 -heteroaryl or heterosubstituents; wherein R 1 and R 2 may be same or different and each stands for a straight chain, branched chain or cyclic aliphatic C 1 to C 20 hydrocarbon, optionally having one or more unsaturated bonds, C 3 -C 8 -heterocycloalkyl, C 6 to C 20 aryl, (C 1 -C 6)-alkyl-C 6 to C 20 -aryl, (C 1 -C 6)-alkyl-C 5 to C 20 -heteroaryl, each hydrocarbon optionally being substituted by one or more groups selected from C 1 to C 20 straight chain, branched chain or cyclic aliphatic hydrocarbons, optionally having one or more unsaturated bonds, C 3 -C 8 -heterocycloalkyl, C 6 to C 20 aryl, (C 1 -C 6)-alkyl-C 6 to C 20 -aryl, (C 1 -C 6)-alkyl-Cs to C 20 -heteroaryl or heterosubstituents; wherein cat Rh I stands for a Tp-Rhodium complex with a mono- or bidentate phosphine, wherein Tp stands for (tris(1-pyrazolyl)borohydride, and wherein solvent stands for an organic solvent, preferably a aprotic polar organic solvent.