In this work, 2,4-bis[4-(N,N-diisobutylamino)-2,6-dihydroxyphenyl] squaraine (SQ) was systematically studied as an electron donor in solution processed photovoltaic cells, showing power conversion efficiency of >4.0% under AM1.5G 1 sun illumination at room temperature. Low mobilities were found to limit charge transport in the bulk heterojunctions. Efficiency was thus improved to 5.1% at 80 °C mainly due to improvement of photocurrent extraction. We also demonstrated that the SQ compound synthesized via a simple method has high purity, and thus can be used in photovoltaic cells without further purification. Our results suggest the huge potential of SQ and its analogs in organic photovoltaic applications.