<p>Organic semiconductor blends offer a promising platform for low-cost and environmental friendly optoelectronic devices, yet their performance is often limited by incomplete spectral absorption and suboptimal charge-transfer characteristics. In this work, we investigate the optical and structural properties of two binary blends (VOPcPhO: PC₇₁BM and PCDTBT: PC₇₁BM) and a ternary blend (VOPcPhO: PCDTBT: PC₇₁BM) to identify the advantages of combining complementary donor materials in a bulk-heterojunction system. The ternary film exhibits markedly enhanced photoactive behavior, achieving a high absorption coefficient of ~ 1.8×10⁵ cm^− 1 at 3.56&#xa0;eV, a refractive index of ~ 2.4, and an extinction coefficient of ~ 3.54 × 10⁴ cm^− 1. Its optical conductivity increases to ~ 6.43 × 10¹⁵ S·cm^− 1, surpassing both binary counterparts. Improved film morphology and favorable energy-level alignment further promote stronger light-matter interaction and more efficient charge-transfer pathways. These combined enhancements demonstrate that the VOPcPhO: PCDTBT: PC₇₁BM ternary blend outperforms the binary systems in both optical response and structural quality, highlighting its strong potential as an effective active layer for next-generation high-performance optoelectronic devices.</p>