We report the morphological characterization of triisopropylsilylethynyl-dibenzochrysene (TIPS-DBC:PCBM) blends, a bulk heterojunction (BHJ) solar cell system based on a highly crystalline small molecule donor. We found that processing the blends from a volatile solvent such as chloroform is beneficial in controlling the crystal size and phase separation of the donor–acceptor phases. When a less-volatile solvent such as chlorobenzene is used, large crystalline domains formed, exceeding the length scale suitable for BHJ solar cells. When the BHJ films are thermally annealed, enhanced domain purity is observed for the chloroform processed thin films, which led to an increased short circuit current in the devices.