In this paper, π-conjugated copolymers, namely N-hexylphenothiazine/cyanopyridine/phenyl/benzothiadiazole, N-hexylphenothiazine/cyanopyridine/phenyl/9,9-dihexylfluorene, and N-hexylphenothiazine/cyanopyridine/phenyl/9,9-diethylhexylfluorene were readily synthesized via Pd-catalyzed Suzuki cross-coupling reaction. The polymer structures and their photophysical properties were characterized by elemental analysis, 1H NMR, GPC, TGA, XRD, UV-vis absorption and PL spectroscopy measurements. The coupling agent effect on photophysical properties of copolymers was investigated to rationally design polymers with particular physical properties to be employed in optoelectronic devices. The UV-vis absorption spectroscopy of copolymers showed λmax at a range of ∼334–474 nm and red-shifted in their films to a range of ∼342–381 nm. These copolymers displayed highly intense fluorescence in their solutions and films. The PL spectra of copolymers indicated red and near-infrared light, rendering them a prospect for being red and near-infrared light-emitting materials for PLEDs. XRD analysis demonstrated a d-spacing range of ∼3.79–4.32 Å, reflecting π-π stacking and some degree of crystallinity in some polymers, and only P1 and P2 showed peaks in the small-angle region, indicating lamellar structures. To understand the relationship between molecular structures of target materials and their photophysical and photovoltaic properties, density functional theory (DFT) and its time-dependent form (TD-DFT) were employed.