We report two new squaraine dyes substituted at the pyrrolic rings with n-hexyl (squaraine 1) or n-hexenyl (squaraine 2) chains. Although internal molecular structure variations are minimal, the presence of the terminal double bond results in a much more compact solid-state structure, dramatically affecting charge transport in the thin films; the hole mobility of 2 is similar to 5x that of 1, and the BHJ OPV power conversion efficiency (PCE) of 2 is similar to 2x that of 1. PCEs surpassing 2% for ambient solution-processed devices are demonstrated, the largest so far achieved for squaraine-based organic solar cells.