The interfaces between n-type silicon (n-Si) and metal electrode contact have enormous influences on the performance and stability of silicon solar cells. Recently, it has been proven that the carrier-selective contact (CSC) is an effective strategy to improve the device efficiency. Herein, a solution-processed and annealing-free zirconium acetylacetonate (ZrAcac) layer is used as an electron-selective contact for fabricating efficient crystalline silicon solar cell. This contact scheme enabled a reduction in both the contact resistivity and the work function at the interface between n-Si and Al, which can be attributed to the dipole formation at the contact interface induced by charge transfer. The application of this ZrAcac based contact was shown to consistently improve all device parameters reaching a maximum power conversion efficiency of 17.8% with a high fill factor of 81.1%, and greatly improve the device stability. This work demonstrated that the ZrAcac layer can provide sufficient energy alignment and enhanced carrier selectivity for efficient and stable photovoltaic devices.