A hollow fiber comprising: a hollow positioned at the center of the hollow fiber, macropores positioned at adjacent to the hollow, and mesopores and picopores positioned at adjacent to macropores wherein the picopores are three dimensionally connected to each other to form a three dimensional network structure, the hollow fiber comprises a thermally rearranged polymer derived from polyamic acid by a heat treatment, and the polyamic acid comprises a repeating unit obtained from dianhydride and aromatic diamine including at least one ortho-positioned functional group with respect to an amine group, wherein the thermally rearranged polymer comprises a polymer represented by one of the following Chemical Formulae 19 to 32, or copolymers thereof: wherein in the above Chemical Formulae 19 to 32, An is an aromatic group selected from a substituted or unsubstituted quadrivalent C6 to C24 arylene group and a substituted or unsubstituted quadrivalent C4 to C24 heterocyclic group, where the aromatic group is present singularly; at least two aromatic groups are fused to form a condensed cycle; or at least two aromatic groups are linked by single bond or a functional group selected from O, S, C(=O), S(=O) 2, Si(CH 3) 2, (CH 2) p (where 1≤p≤10), (CF 2) q (where 1≤q≤10), C(CH 3) 2, C(CF 3) 2, or C(=O)NH, Ar 1 ' and Ar 2 are the same or different, and independently an aromatic group selected from a substituted or unsubstituted divalent C6 to C24 arylene group and a substituted or unsubstituted divalent C4 to C24 heterocyclic group, where the aromatic group is present singularly; at least two aromatic groups are fused to form a condensed cycle; or at least two aromatic groups are linked by single bond or a functional group selected from O, S, C(=O), S(=O) 2, Si(CH 3) 2, (CH 2) p (where 1≤p≤10), (CF 2) q (where 1≤q≤10), C(CH 3) 2, C(CF 3) 2, or C(=O)NH, Q is O, S, C(=O), CH, S(=O) 2, Si(CH 3) 2, (CH 2) p (where 1≤p≤10), (CF 2) q (where 1≤q≤10), C(CH 3) 2, C(CF 3) 2, C(=O)NH, C(CH 3)(CF 3), or a substituted or unsubstituted phenylene group (where the substituted phenylene group is a phenylene group substituted with a C1 to C6 alkyl group or a C1 to C6 haloalkyl group), where the Q is linked with aromatic groups with m-m, m-p, p-m, or p-p positions, Y" is O or S, n is an integer ranging from 20 to 200, m is an integer ranging from 10 to 400, I is an integer ranging from 10 to 400, and wherein the hollow fiber comprises a dense layer including picopores at a surface portion. a hollow positioned at the center of the hollow fiber, macropores positioned at adjacent to the hollow, and mesopores and picopores positioned at adjacent to macropores wherein the picopores are three dimensionally connected to each other to form a three dimensional network structure, the hollow fiber comprises a thermally rearranged polymer derived from polyamic acid by a heat treatment, and the polyamic acid comprises a repeating unit obtained from dianhydride and aromatic diamine including at least one ortho-positioned functional group with respect to an amine group, An is an aromatic group selected from a substituted or unsubstituted quadrivalent C6 to C24 arylene group and a substituted or unsubstituted quadrivalent C4 to C24 heterocyclic group, where the aromatic group is present singularly; at least two aromatic groups are fused to form a condensed cycle; or at least two aromatic groups are linked by single bond or a functional group selected from O, S, C(=O), S(=O) 2, Si(CH 3) 2, (CH 2) p (where 1≤p≤10), (CF 2) q (where 1≤q≤10), C(CH 3) 2, C(CF 3) 2, or C(=O)NH, Ar 1 ' and Ar 2 are the same or different, and independently an aromatic group selected from a substituted or unsubstituted divalent C6 to C24 arylene group and a substituted or unsubstituted divalent C4 to C24 heterocyclic group, where the aromatic group is present singularly; at least two aromatic groups are fused to form a condensed cycle; or at least two aromatic groups are linked by single bond or a functional group selected from O, S, C(=O), S(=O) 2, Si(CH 3) 2, (CH 2) p (where 1≤p≤10), (CF 2) q (where 1≤q≤10), C(CH 3) 2, C(CF 3) 2, or C(=O)NH, Q is O, S, C(=O), CH, S(=O) 2, Si(CH 3) 2, (CH 2) p (where 1≤p≤10), (CF 2) q (where 1≤q≤10), C(CH 3) 2, C(CF 3) 2, C(=O)NH, C(CH 3)(CF 3), or a substituted or unsubstituted phenylene group (where the substituted phenylene group is a phenylene group substituted with a C1 to C6 alkyl group or a C1 to C6 haloalkyl group), where the Q is linked with aromatic groups with m-m, m-p, p-m, or p-p positions, Y" is O or S, n is an integer ranging from 20 to 200, m is an integer ranging from 10 to 400, I is an integer ranging from 10 to 400, and wherein the hollow fiber comprises a dense layer including picopores at a surface portion.