Heteroaromatic cations reacted with N-heteroarylacetylenes under Sonogashira conditions to allow easy access to potential single donor D-π-A⁺ and V-shaped D-π-A⁺-π-D chromophores, where the acceptor moiety A is the π-deficient pyridinium cation and the donor moiety is represented by different π-excessive N-heterocycles. The β hyperpolarizabilities were measured using hyper-Rayleigh scattering experiments and the experimental data are supported by a theoretical analysis that combines a variety of computational procedures, including Density Functional Theory (DFT) and correlated Hartree–Fock-based methods (RCIS(D)).