Transition metal oxides (TMOs) have recently been proved to efficiently serve as hole-selective contacts in crystalline silicon (c-Si) heterojunction solar cells. In the present work, two TMO/c-Si heterojunctions are explored using MoO3 (reference) and V2O5 as an alternative candidate. It has been found that V2O5 devices present larger (16% improvement) power conversion efficiency mainly due to their higher open-circuit voltage. While V2O5/c-Si devices with textured front surfaces exhibit larger short-circuit currents, it is also observed that flat solar cell architectures allow for passivation of the "1205/n-Si interface, giving significant carrier lifetimes of 200 mu s (equivalent to a surface recombination velocity of S-eff similar to 140 cm s(-1)) as derived from impedance analysis. As a consequence, a significant open-circuit voltage of 662 mV is achieved. It is found that, at the TMO/c-Si contact, a TMO work function enhancement Delta phi(TMO) occurs during the heterojunction formation with the consequent dipole layer enlargement Delta'=Delta+Delta phi(TMO). Our results provide new insights into the TMO/c-Si contact energetics, carrier transport across the interface and surface recombination allowing for further understanding of the nature of TMO/c-Si heterojunctions.