A series of thiophenic monomers functionalized with different chromophoric groups have been optically characterized in view of preparation of polymeric films for second-order nonlinear optics and electroopics. In order to investigate the optical behaviour inside a solid host matrix, the molecules have been physically dispersed in poly(methylmethaerylate) (PMMA) films and poled through high-temperature corona-poling for characterization through in situ second harmonic generation and ex situ angle-resolved spectroscopy. The values of dipole moment mu and optical hyperpolarizability beta have been estimated inside the host matrix and related to the molecular structure. For one of the chromophores the long-term reorientation dynamics has been monitored in order to investigate the stability and the interaction with the polymeric environment.