Renewable energy can effectively decrease carbon-dioxide emissions, and alleviate the Greenhouse effect. For consuming huge fossil fuel, Taiwan does have the obligation to reduce carbon-dioxide emissions. For the sunshine abound in the whole island and mature of photovoltaic (PV) industry, Taiwan has the potential to develop PV. This paper based on the Theory of Planned Behavior (TPB) and Multi-perspective on Technological Transition (MLP) focuses on the PV evolution of Taiwan. By empirical study, this paper developed a research framework, and applied questionnaire survey to verify it. Further, this paper also has a longitudinal case study and by historical research method to explore the evolution of Taiwan¡¦s PV policy. This paper found that attitude is the primary factor that affects the household¡¦s attention, and its antecedent factor relative advantage is the most important one. The second factor that affects the household¡¦s intention is perceived behavioral control which has the antecedent factor complexity. Further, perceived behavioral control also has the direct effect to the action which we must pay attention to it. Subjective norm has slight effect to the household¡¦s intention. And, social obligation is the antecedent factor of the subjective norm. Moreover, interfere effect exists between intention and household¡¦s real action. From the macro prospective, MLP depicts the evolution of Taiwan¡¦s PV diffusion, and we found it was resulted from the interaction of socio-technical landscape, socio-technical regime and niche-innovation. The processes were continually developed and form an innovative technology spiral.