Summary: Condensation polymers based on two different NLO‐active chromophores, namely 2‐[4‐[(4‐N,N‐dihydroxyethylamino)phenylazo]phenyl]‐5(6)‐nitrobenzimidazole (BZI) and 2‐[4‐(4‐N,N‐dihydroxyethylamino)phenylazo]‐4,5‐dicyanoimidazole (IMI), have been synthesized and their basic properties measured. The second order NLO properties of poled polymers were investigated by SHG procedures at different temperatures (35, 65 and 85 °C) and exposure times. Resonance free d33 coefficients (λ = 1 368 nm) took values in the range 1.8–4.0 pm · V−1, but the time stability of their SHG signal was fairly acceptable, particularly for the high Tg (e.g. 188 °C) polymer for which a relaxation time (at 25 °C) of 2.8 years has been determined.