Density functional theory (DFT) B3LYP method was employed to calculate electron properties and the second-order nonlinear optical (NLO) responses of the derivatives which were formed by (C 5 H 5 )Co(C 2 B 4 H 6 ) and CHCHC 6 H 4 NO 2 , CHCHC 6 H 4 NH 2 . The results show: when H atom of (C 5 H 5 )Co(C 2 B 4 H 6 ) is substituted by CHCHC 6 H 4 NO 2 , the β tot values of isomers are all slightly smaller than that of ferrocene (Fc) derivative (FcCHCHC 6 H 4 NO 2 ). However, when H atom of (C 5 H 5 )Co(C 2 B 4 H 6 ) is substituted by CHCHC 6 H 4 NH 2 , the β tot values of isomers are close to that of ferrocene (Fc) derivative (FcCHCHC 6 H 4 NH 2 ). It indicates that (C 5 H 5 )Co(C 2 B 4 H 6 ) can be either a donator or an acceptor.