Water-based nanoparticulate (NP) and bulk heterojunction (BHJ) organic photovoltaic (OPV) devices based on blends of poly(9,9-dioctylfluorene-co-N,N-bis(4-butylphenyl)-N,Ndiphenyl-1,4-phenylenediamine) (PFB) and poly(9,9-dioctylfluorene-co-benzothiadiazole (F8BT) have been fabricated with aluminium and calcium/aluminium cathodes. The NP devices exhibit power conversion efficiencies (PCEs) that are double that of the corresponding BHJ device. Moreover, the addition of calcium into the cathode structure results in a dramatic increase in open circuit voltage and PCEs approaching 1% for water-based polyfluorene OPV devices.