The block-scale application of photovoltaic technology in cities is becoming a viable solution for renewable energy utilization. The rapid urbanization process has provided urban buildings with a colossal development potential for solar energy in China, especially in industrial areas that provide more space for the integration of PV equipment. In developing solar energy resources, the block layout and the PV materials are two critical factors affecting the distribution of solar radiation and generation. However, few studies have analyzed how to select the most suitable PV materials for different layouts of industrial blocks to obtain the best generation. This study considered the layout of industrial blocks and PV materials simultaneously, and the generation yield was calculated when combined. A total of 40 real industrial block cases were constructed, and radiation distribution data on building surfaces of different block cases were calculated. Data on both were combined to calculate the generation of different PV materials for each block type. The findings indicated that single-story industrial blocks possessed the highest potential for solar radiation, primarily due to the higher percentage of roof area. The influence of PV materials on the installation rate of different building facades varied, with the installation rate of the west facade being the most impacted by PV performance and the roof being the least impacted. Using different PV materials in industrial blocks could lead to a 59.2% difference in solar generation capacity. For single-layer industrial blocks, mono crystalline and poly crystalline silicon were preferable to achieve higher power generation. In contrast, multi-story and high-rise industrial blocks were best suited for a-Si and CIGS to attain higher cost performance. The methods and results of this study guided the selection and installation of PV equipment in various block typologies, thereby improving the refinement of solar resource development, maximizing solar resource utilization, and promoting the development of energy conservation and carbon reduction in cities.