The paper applies the evolutionary game theory to technological innovation strategy of photovoltaic enterprises. The study establishes the model of game and solves its evolutionary stable strategy (ESS). By analyzing the ESS, we get some useful results. The results indicate that enterprise's strategic selection depends on the proportion of strategies. When the proportion of independent innovation is higher than the critical value, photovoltaic enterprise adopts the independent innovation strategy. Conversely, enterprise adopts the cooperative innovation strategy. Finally, the paper puts forward some suggestions on the technological innovation strategies of photovoltaic enterprise.