The geometrical structure and stability of neutral pi-conjugated C4H4N center dot with three spin states were investigated by using ab initio and density functional theory (DFT) methods. In addition, the linear and nonlinear optical properties were studied at the same level combined with the finite field approach. The calculated results show that conjugation and stability decreased with increasing spin multiplicity. These reliable UCCSD results show that the polarizability (alpha) values Of C4H4N center dot with the quartet state are maximal, while those of C4H4N center dot with the doublet state are minimal. The order of beta(tot) values is beta(sextet) > beta(doublet) > beta(quartet). The second hyperpolarizability (gamma) values exhibit positive values. The variation trends of gamma are consistent with alpha.