Various hybrid functionals (B3LYP, B97-2, PBE0, BMK, BH&HLYP, CAM-B3LYP, and LC-xPBE) implemented in density functional theory were applied to give estimate of static first hyperpolarizabilty (b 0 ) of (E)benzaldehyde phenylhydrazone designated as (E)-BPH. Against those of MP2 computations as a function of the underlying density functional, good agreement was obtained with the BH&HLYP and CAM-B3LYP functionals. The LC-xPBE functional and the B3LYP, PBE0, B97-2, and BMK functionals underestimated and overestimated b 0 , respectively. The basis set effect on the calculated b 0 was also investigated. It turned out that the 6-3111G(2d,p) basis set provided excellent converged value of b 0 . On the basis of the calculated results, we investigated the substituent effect on b 0 of donor-acceptor (D-A) substituted (E)-BPH systematically by using the BH&HLYP and CAM-B3LYP computations with the 6-3111G(2d,p) basis set. We proposed a Zwitterion structure to explain the calculated trend in the substituent effect and the enhanced hyperpolarizability of type II compounds (A-(E)-BPH-D) than type I compounds (D-(E)-BPH-A). Natural bonding orbital analysis carried out at BH&HLYP/ 6-3111G(2d,p)//B3LYP/6-31G(2df,p) level of theory substantiated the claim.