In this work, two thermal- and air-stable, hole transporting materials (HTM) in perovskite solar cells are analyzed. Those obtained and investigated materials were two polyazomethines: the first one with three thiophene rings and 3,3’-dimethoxybenzidine moieties (S9) and the second one with three thiophene rings and fluorene moieties (S7). Furthermore, presented polyazomethines were characterized by Fourier transform infrared spectroscopy (FTIR), UV–vis spectroscopy, atomic force microscopy (AFM) and thermogravimetric analysis (TGA) experiments. Both polyazomethines (S7 and S9) possessed good thermal stability with a 5% weight loss at 406 and 377°C, respectively. The conductivity of S7 was two orders of magnitude higher than for S9 polymer (2.7 × 10⁻⁸ S/cm, and 2.6 × 10⁻¹⁰ S/cm, respectively). Moreover, polyazomethine S9 exhibited 31 nm bathochromic shift of the absorption band maximum compared toS7. Obtained perovskite was investigated by UV–vis and XRD. Electrical parameters of perovskite solar cells (PSC) were investigated at Standard Test Conditions (STC). It was found that both polyazomethines protect perovskite which is confirmed by ageing test where Voc did not decrease significantly for solar cells with HTM in contrast to solar cell without hole conductor, where Voc decrease was substantial. The best photoconversion efficiency (PCE = 6.9%), among two investigated in this work polyazomethines, was obtained for device with the following architectures FTO/TiO₂/TiO₂ + perovskite/S7/Au. Stability test proved the procreative effects of polyazomethines on perovskite absorber.