Tetracyanobutadiene (TCBD)-derived π-chromic materials have gained momentum in electronic and photonic devices. Owing to their unique optoelectronic and structural characteristics, they further hold promise as active layer materials for granting access to futuristic organic solar cells (OSCs). In the present contribution, three TCBD-based electron donors (13–15) were synthesized by strategizing π-bridge extension along with the investigation of their opto-electrochemical and other functional properties. Exploiting the merger of these chromophores with near-IR absorbing 2,4-bis[4-(N,N-diphenylamino)-2,6-dihydroxyphenyl] squaraine (DPSQ) additive promotes an enhanced light harvesting property. Prototype OSCs fabricated with a ternary blend composed of 13–15, PC61BM, and DPSQ showed an improved efficiency of 9.8%. Apparently, a comparative evaluation of additive loading in influencing the photovoltaic parameters is remarked. On a larger picture, this work validates the synergy of π-spacing and external additives in augmenting the photovoltaic properties of TCBD-based electron donors.