A series of divinyl-pyrene derivatives of the form D-vinyl-pyrene-vinyl-A, in which D corresponds to an electron donor group and A to an electron acceptor group, were studied in this work. The first purpose was to determine the optimal HF % exchange as incorporated in a range of hybrid functionals (M06HF, M062X, M06L, CAM-B3LYP, PBEO, BMK, and B3LYP) capable to produce, reliably and as close as possible to those obtained from MP2 calculations, NLO parameters and, in particular, first-order static hyperpolarizabilities. The CAM-B3LYP functional was revealed to be the most suitable one. The pair N(CH3)(2)/NO2 was then determined as the most efficient pair of groups in producing appreciable NLO responses. The effect of the substitution position on the pyrene moiety was also investigated, whereby aligning the two substituents involving the D and A groups in the direction of the dipole moment as in the (1,6 DVP) derivatives was shown to be most favorable for increasing the NLO parameters.