Two random (ZnII-based P1P2) and two alternating (RuII-based P3P4) metallo-copolymers containing bis-terpyridyl ligands with various central donor (i.e., fluorene or carbazole) and acceptor (i.e., benzothiadiazole) moieties were synthesized. The effects of electron donoracceptor interactions with metal (ZnII and RuII) ions on their thermal, optical, and electrochemical properties were investigated. Because of the strong ICT transitions between donor and acceptor ligands in both ZnII- and RuII-based metallo-coplymers and MLCT transitions in RuII-based metallo-coplymers, the absorption spectra covered a broad range of 260750 nm with the band gaps of 1.571.77 eV. In addition, the introduction of RuII-based metallo-coplymer P4 mixed with PC60BM as an active layer of the BHJ solar cell device exhibited the highest PCE value up to 0.90%.