We report both transport measurements and spectroscopic data of polymer/fullerene blend photovoltaics using a small library of fullerene esters to correlate device properties with a range of functionality and structural diversity of the ester substituent. We observe that minor structural changes can lead to significant and surprising differences in device efficiency and lifetime. For example we have found that isomeric R-groups in the fullerene ester-based devices we have studied have dramatically different efficiencies. The characteristic lifetimes derived from both transport and spectroscopic measurements are generally comparable; however, some more rapid effects in specific fullerene esters are not observed spectroscopically. It is apparent from our results that each fullerene derivative requires re-optimization to reveal the best device performance. Furthermore we conclude that a library approach is essential for evaluating the effects of structural differences in the constituent molecules and serves as important device optimization method that is not being currently employed in photovoltaic investigations. Copyright (c) 2015 John Wiley & Sons, Ltd.