Solution-processed cadmium telluride (CdTe) nanocrystal (NC) solar cells offer the advantages of low cost, low consumption of materials and large-scale production via a roll-to-roll manufacture process. Undecorated CdTe NC solar cells, however, tend to show inferior performance due to the abundant crystal boundaries within the active CdTe NC layer. The introduction of hole transport layer (HTL) is effective for promoting the performance of CdTe NC solar cells. Although high-performance CdTe NC solar cells have been realized by adopting organic HTLs, the contact resistance between active layer and the electrode is still a large problem due to the parasitic resistance of HTLs. Here, we developed a simple phosphine-doping technique via a solution process under ambient conditions using triphenylphosphine (TPP) as a phosphine source. This doping technique effectively promoted the power conversion efficiency (PCE) of devices to 5.41% and enabled the device to have extraordinary stability, showing a superior performance compared with the control device. Characterizations suggested that the introduction of the phosphine dopant led to higher carrier concentration, hole mobility and a longer lifetime of the carriers. Our work presents a new and simple phosphine-doping strategy for further improving the performance of CdTe NC solar cells.