A few new phenoxazine-based conjugated monomers were synthesized, characterized, and successfully used as semiconducting materials. The phenoxazine-based oligomers have low ionization potentials or high-lying HOMO levels (~4.7 eV), which were estimated from cyclic voltammetry. Conjugated oligomers offer good film-forming, mechanical and optical properties connected with their wide application. These results demonstrate that phenoxazine-based conjugated mers are a promising type of semiconducting and luminescent structures able to be used as thin films in organic electronics.