The polycondensation of 5,5-methylene bis(2-aminophenol) and the mixture of diamines 5,5-methylene bis(2-aminophenol) and 4,4-(hexafluoroisopropylidene)dianiline (molar ratio 0.8:0.2) with isophthaloyl dichloride was used to synthesize a new heat resistant binder of the composites for microelectronics: poly(o-hydroxyamide) (POA) and poly(amido-o-hydroxy amide) (POA-F). The thermal stability of synthesized polymer coatings, as well as based on them photosensitive compositions with a naphthoquinondiazide photosensitive component were studied in the temperature range from 100 to 500 °C. Ferroelectric composites with nanodispersed lead titanate zirconate powder filler were formed based on these polymer matrices. By manipulating the conditions of the polymer formation, we obtained matrices with different stiffnesses, which reflected on the properties of the composite. The electrophysical parameters of the synthesized polymer and ferroelectric composite coatings were measured in the frequency range from 0.1 Hz to 1.5 GHz and the temperature range from 0 to 300 °C. The frequency and temperature stability of the dielectric constant of ferroelectric composite coatings up to 10 MHz and 300 °C, respectively, are noted. The influence of the composition and structure of the polymer matrix and the grain/matrix interfaces on the thermal stability of the dielectric parameters of composite films is estimated. The shift of the phase transition region toward higher temperatures in the composite structure, as well as the sufficient rigidity of the poly(benzoxazole) matrix, provide high temperature and frequency stability of the dielectric constant of the studied composites.