Dopant-free carrier-selective contacts are becoming increasingly attractive for application in silicon solar cells because of the depositions for their fabrication being simpler and occurring at lower temperatures. However, these contacts are limited by poor thermal and environmental stability. In this contribution, the use of the conductive high work function of cuprous iodide, with its characteristic thermal and ambient stability, has enabled a hole-selective contact for p-type silicon solar cells because of the large conduction band offset and small valence offset at the CuI/p-Si interface. The contact resistivity (≈30 mΩ·cm) of the Ag/CuI (20 nm)/p-Si contact after annealing to 200 °C represents the CuI-based hole-selective contact with low resistance and high thermal stability. Microscopic images and elemental mapping of the Ag/CuI/p-Si contact interface revealed that a nonuniform, continuous CuI layer separates the Ag electrode and p-type Si. Thermal treatment at 200 °C results in the intermixing of the Ag and CuI layers. As a result, the 200 °C thermal process improves the efficiency (20.7%) and stability of the p-Si solar cells featuring partial CuI hole-selective contact. Furthermore, the devices employing the CuI/Ag contact are thermally stable upon annealing to temperatures up to 350 °C. These results not only demonstrate the use of metal iodide instead of metal oxides as hole-selective contacts for efficient silicon solar cells but also have important implications regarding industrial feasibility and longevity for deployment in the field.