The incorporation of trityl and triphenylsilyl groups into low molecular weight molecules allows the formation of stable molecular glasses. A series of materials based on the N-phenyldiethanolamine core was synthesized bearing different azobenzenes and benzylydene-1,3-indandione as active chromophores. Molecular hyperpolarizability of the synthesized compounds was calculated by a restricted Hartree–Fock method with basis 6-31G(d,p) and measured in solutions by hyper-Rayleigh scattering. Non-linear optical (NLO) activity of the thin glassy films was confirmed after a corona poling procedure. Thermal sustainability of the NLO response of up to 85 C was achieved. Quantum chemical calculations of the compounds revealed increased steric bulk and conformational freedom of the triphenylsilyl moiety. While the presence of the triphenylsilyl group results in more stable glasses and increased material nonlinearity, in the case of trityl groups, measured glass transition temperatures are higher.