Abstract Functionalized photochromic materials have attracted a growing interest during the last few decades since they are promising materials to be used in optoelectronics and photonics. In this paper, the results of the nonlinear optical (NLO) investigation (second and third harmonic generation) of spin deposited high-quality thin films of styrylquinoline containing methacrylic polymers studied by using Maker fringes technique employing 30 ps laser pulses at fundamental wavelength of 1064 nm are presented. Photochromic styrylquinoline units were oriented in the thin films by corona poling technique promoting second order NLO activity. Strong dependence of the NLO response upon the structure of the polymers has been found, which is related to the different charge transfer within the styrylquinoline fragments. These investigations were completed by theoretical studies using HOMO-LUMO energy levels theory and the first and second order hyperpolarizability values. Good compatibility has been achieved between the theoretical and experimental results. Studied styrylquinoline-based polymers showed the contrast in NLO response after their trans-cis photoisomerization making them interesting for using in photonic devices.