High-performance passivating contact is a prerequisite for high-efficiency crystalline silicon (c-Si) solar cells. In this work, an electron-conductive, hole-blocking contact based on titanium nitride (TiN) deposited by reactive magnetron sputtering is presented. Quasi-metallic TiN combined with an ultrathin SiO2 passivation layer (SiO2/TiN) is demonstrated to be an effective electron-selective contact on c-Si, featuring a low-contact resistivity of 16.4 mΩ.cm2 and a tolerable recombination current parameter of ∼500 fA/cm2. By implementing the dual-function SiO2/TiN contact, which acts simultaneously as a surface passivating layer and metal electrode, an efficiency of 20% is achieved by an n-type c-Si solar cell with a simple structure. This work not only demonstrates a way to develop efficient n-type c-Si solar cells with dual-function metal nitride contacts at a low cost but also expands the pool of available carrier transport materials, from metal oxides to metal nitrides, for photovoltaic devices.