Photovoltaic poverty alleviation power stations (PPAPS) are the foundation of poverty alleviation, whose operation and maintenance (O&M) status is the key to ensuring long-term poverty reduction advantages. As part of PPAPS′ O&M performance, the role of the O&M contracts has yet to be proven. This paper uses a three-stage data envelopment analysis (DEA) model and grey relation analysis (GRA) to analyze the O&M performance efficiency of PPAPS and the influencing factors of contract governance from field data of 110 counties in Henan Province, China. The results show that:1) the O&M efficiency of the PPAPS is relatively high and inconsistent across the region, which has not yet attained optimal productivity; 2) the present efficiency is mainly determined by the initial investment size and installed capacity; 3) the governance factors of O&M contracts affect the performance efficiency of PPAPS, which may lead to overestimation; and 4) longer contract term and higher performance incentive coefficients may result in inefficiencies at the initial stage of PPAPS′ use, while government subsidies allocation and timely O&M cost settlement have little impact on O&M efficiency. This paper proposes corresponding policy recommendations finally.