Recent work has pointed to polymer miscibility and surface energy as key figures of merit in the formation of organic alloys and synergistic behavior between components in ternary blend solar cells. Here, we present a simple model system and first report of poly(3-hexylthiophene)-based random copolymers featuring either a semifluoroalkyl (P3HT-co-FHT) or oligoether (P3HT-co-MET) side chain, prepared via Stille polycondensation. Water drop contact angle measurements demonstrated that P3HT-co-FHT polymers reached a minimum surface energy of 14.2 mN/m at 50% composition of comonomers, while in contrast, P3HT-co-MET polymers increased as high as 27.0 mN/m at 50% composition, compared to P3HT at 19.9 mN/m. Importantly, the surface energy of the copolymers was found to vary regularly with comonomer composition and exhibited fine-tuning. Optical and electronic properties of the polymers are found to be composition independent as determined by UV-vis and CV measurements; HOMO energy levels ranged from 5.25 to 5.30 eV; and optical band gaps all measured 1.9 eV. Following this model, surface energy modification of state-of-the-art polymers, without altering desirable electronic and optical properties, is proposed as a useful tool in identifying and exploiting more alloying polymer pairs for ternary blend solar cells.