To explore the law of coupling coordination development of China’s photovoltaic (PV) agriculture system, this study measured the comprehensive development level of the agriculture and PV industries from 2007 to 2016 using China’s agricultural and photovoltaic industry statistics. Once this was achieved, the coupling coordination degree of the PV agricultural system was measured and a development mode of this system was determined. Finally, we explored the development trend of the coupled and coordinated evolution of the system. The main research results show that: (1) Although the development level of the agriculture and PV industries are both in an upward trend, the rising rate of development by the PV industry far exceeds the agriculture industry. (2) As agricultural and PV industries expand, they both show stock resource-led characteristics, but the incremental resources of the PV industry are gradually taking the lead. (3) The coupling coordination degree of the agriculture and PV industries fluctuates as it rises, but the coupling is low. It has not yet evolved to a higher level of coupling, and the speed of upgrading and evolution is slow. (4) In the next 10 years, the evolution speed of the two industries will be significantly improved, and the coupling between them will enter the coordination stage. PV agriculture will further develop in a sustainable direction.