This paper describes the synthesis and characterization of new organic semiconductors based on pyrrolo[1,2-i][1,7]phenanthrolines in the form of thin layers. The thin layers, produced via the spin coating method (with a thickness of 10–11 μm), were investigated for their electrical and optical properties. After heat treatment at temperatures ranging from 210 to 240 °C, the layers displayed consistent and reproducible properties. The layers exhibited n-type semiconductor behavior, with a thermal activation energy (Ea) in the range of 0.75–0.78 eV. Additionally, the layers showed transmittance values of 84–92% in the visible and near-infrared spectral ranges, with a direct optical band gap (Egod) ranging from 3.13 to 4.11 eV. These thin layers have potential applications in electronic devices such as thermistors, as well as in nanoelectronics and optoelectronics. Overall, these new organic semiconductors show promising properties for practical implementation in various electronic applications.