Solution-processed small-molecule bulk heterojunction photovoltaic cells are fabricated by using [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) as electron acceptor and triisopropylsilylethynyl anthracene (TIPSAnt) derivatives substituted with naphthalene (TIPSAntNa) and bithiophene (TIPSAntBT) as electron donors. In contrast to TIPS–pentacene, the TIPSAnt derivatives are not susceptible to Diels–Alder reactions with PCBM when processed in solution, as confirmed by UV/Vis measurements. Photoluminescence quenching measurements show exciton diffusion lengths of 5 and 3 nm for TIPSAntBT and TIPSAntNa, respectively. Blending TIPSAntBT and TIPSAntNa with PCBM (1:1, 1:2, 1:3, and 1:4 weight ratios) produces films that possess adequate hole and electron mobilities. The morphological changes that result from varying the blending ratio range from obvious phase-segregated crystalline domains at a 1:1 ratio to homogeneous, nearly amorphous phases at a 1:4 ratio. Bulk heterojunction solar cells prepared by using a TIPSAntBT:PCBM blend reach power conversion efficiencies as high as 1.4 %.