Abstract Novel, asymmetrically shaped, pyrrole-based polyene chromophores were designed to obtain a large angle θ ( μ , β max ) between the directions of the maximum first hyperpolarizability β max and the dipole moment μ , by introducing an asymmetric core pyrrole into the π-conjugated polyene bridge of the chromophore. Asymmetric N -substituted pyrrolic nonlinear optical chromophores based on configurationally locked polyene (CLP) were synthesized and their first hyperpolarizabilities were theoretically determined using density functional theory (DFT). High asymmetry with an angle θ ( μ , β max ) between the dipole moment μ and the main direction of the charge-transfer transition β max of up to 48° was achieved.