In this work, we use an electron-selective titanium dioxide (TiO2) heterojunction contact to silicon to block minority carrier holes in the silicon from recombining at the cathode contact of a silicon-based photovoltaic device. We present four pieces of evidence demonstrating the beneficial effect of adding the TiO2 hole-blocking layer: reduced dark current, increased open circuit voltage (VOC), increased quantum efficiency at longer wavelengths, and increased stored minority carrier charge under forward bias. The importance of a low rate of recombination of minority carriers at the Si/TiO2 interface for effective blocking of minority carriers is quantitatively described. The anode is made of a poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) heterojunction to silicon which forms a hole selective contact, so that the entire device is made at a maximum temperature of 100 °C, with no doping gradients or junctions in the silicon. A low rate of recombination of minority carriers at the Si/TiO2 interface is crucial for effective blocking of minority carriers. Such a pair of complementary carrier-selective heterojunctions offers a path towards high-efficiency silicon solar cells using relatively simple and near-room temperature fabrication techniques.