Surface recombination represents a handicap for high-efficiency solar cells. Surface recombination represents a handicap for high-efficiency solar cells. This is especially important for nanowire array solar cells, where the surface-to-volume ratio is greatly enhanced. Here, the effect of different passivation materials on the effective recombination and on the device performance is experimentally analyzed. Our solar cells are large area top-down axial n–p junction silicon nanowires fabricated by means of Near-Field Phase-Shift Lithography (NF-PSL). We report an efficiency of 9.9% for the best cell, passivated with a SiO2/SiNx stack. The impact of the presence of a surface fixed charge density at the silicon/oxide interface is studied.