As one of the most rapidly developing provinces in China in the past two decades, Anhui Province has seen an increasing demand for clean energy in recent years due to industrial transformation and the requirements of dual carbon targets. This paper opts to investigate roof-mounted distributed photovoltaics, which are more suitable for development in densely populated areas. Current research on distributed photovoltaics largely focuses on vague estimations of power generation potential, without adequately considering the specific development conditions of different regions. This paper starts from the actual situation affecting the development of roof-mounted distributed photovoltaics and selects a smaller number of factors that are more in line with reality for hierarchical analysis, constructing a relatively simple but practical evaluation system (“meteorological-geographical-socio-economic”). At the same time, this paper innovatively proposes different schemes for the full lifecycle power generation and emission reduction benefits of roof-mounted distributed photovoltaics and compares them, providing a foundation for subsequent in-depth research. Key findings include the following: The northern regions of Anhui Province exhibit higher suitability for rooftop distributed PV, with residential areas being the primary influencing factor, followed by solar radiation considerations; the annual power generation potential of rooftop distributed PV in Anhui Province constitutes around 80% of the total electricity consumption in 2021, but the potential is predominantly concentrated in rural areas, resulting in spatial disparities in power generation and consumption across the province; developing the rooftop distributed PV industry based on suitability can yield substantial power generation and emission reduction benefits, translating to an estimated reduction of approximately 1.28 × 108 tCO2 annually, representing around one-third of Anhui Province’s carbon emissions in 2021.