Unlike the previous several investigations on planar donor-π-acceptor chromophores, the present investigation highlights the importance of twisted molecular configurations to effectively tune the optical and nonlinear optical (NLO) response properties. A variety of substitutions are made to design several twisted molecular compounds (1-7). These compounds are designed using pyrenyl and naphthalimide moieties, which are twisted with each other in their molecular configurations. The calculated versus experimental highest intensity absorption energy peaks (3.482 Vs. 3.444 eV) and experimental ionization potentials (6.07 Vs. 5.93 eV) of parent compound 1 reproduced reasonably well at M06/6-311G** level of theory. The twisted chromophores show significantly larger amplitudes of third-order NLO polarizabilities (<γ>), which are found to be as large as 778.31×10-36 esu for compound 7 at the M06/6-311G