Rooftop solar micro-power plants mitigate pollution and transmission problems in crowded Indian cities. The Indian government is exploring alternate solutions, and the micro, small, and medium enterprises (MSME) sector is also coming forward to opt for sustainable solutions. This study is focused on the MSME segment in India, which constitutes approximately 63 million entities. Installing a solar system for which a rooftop could be the best place to tap solar energy from these entities is required. Checking the rooftop solar potential of any MSME entity requires a suitable technique to decide which sector to target first and the further order. A unique methodology based on multi-criteria decision-making (MCDM) methods is presented to rank 10 MSME alternatives with seven criteria. It includes the measurement of alternatives and ranking according to compromise solution (MARCOS) to rank MSME sectors in India with rooftop solar potential. Weights of importance are assigned with three objective techniques and combined with the Bonferroni operator. The ranks attained are compared with different MCDM methods, and sensitivity analysis is performed while changing weights. Kendall and Spearman rank correlation coefficients are utilized to access the correlation levels between various strategies. Finally, Garrett’s ranking technique is used to finalize the different ranks. The results reveal that the MARCOS method performed well, and “textiles” ranks first, followed by “auto and engineering products.” As a result, the leading industrial sectors will help improve energy utilization while concentrating on renewable energy resources.