This study presents the design and synthesis of two new semiconducting polymers, P1 and P2, incorporating anthracene and tetrazole units. The polymers were obtained via click chemistry with a yield of 60–65 % and fully characterized by nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FT-IR) and thermogravimetric analysis (TGA), confirming their structures and thermal stability up to 250 °C. Optical and electrochemical measurements revealed band gaps of 2.69 eV for P1 and 2.77 eV for P2. Photoluminescence studies showed that P1 emits yellow fluorescence due to intramolecular anthracene interactions, while P2 displays blue light. Cyclic voltammetry indicated n-type semiconductor behavior, and single-layer diodes fabricated from these materials exhibited low turn-on voltages of 3.4–4.5 V. Density functional theory (DFT) calculations combined with the quantum theory of atoms in molecules (QTAIM) and reduced density gradient (RDG) analyses, supported the experimental results and provided insights into the electronic structure and intramolecular interactions. Overall, this work highlights how molecular engineering strategies can be used to precisely tune the optoelectronic properties of semiconducting polymers for applications in light-emitting devices.