Microwave pyrolysis of corn stover has been optimized by Response surface methodology under different microwave power (500, 700, and 900 W) and three ratios of activated carbon additive (10, 15, and 20%) for obtaining maximum bio-oil yield followed by biochar. The optimal result has been evaluated and the environmental and techno-economic impacts of using solar-powered microwave heating have been tested. The optimal pyrolysis condition found to be 700 W microwave power and 10% of activated carbon. The yields of both bio-oil and biochar were about 74 wt% under optimal condition. The higher heat values of 26 MJ/kg and 16 MJ/kg were respectively achieved for biochar and bio-oil. The major components of bio-oil were hydrocarbons (36%) and phenols (28%) with low oxygen-containing compounds (2%) and acids (2%). Using the solar-powered system, 20,549 tonnes of CO₂ can be mitigated over the lifetime of the set-up, resulting in USD 51,373 in carbon credit earnings, compared to 16,875 tonnes of CO₂ mitigation and USD 42,167 in carbon credit earnings from a grid electricity system. The payback periods for solar-powered and grid-connected electrical systems are estimated to be 1.6 and 0.5 years, respectively, based on biochar and bio-oil income of USD 39,700 and USD 45,400.