Methanol is considered a sustainable alternative energy source due to its ease of storage and high-octane rating. However, the conventional methanol production process is accompanied by resource consumption and significant greenhouse gas emissions. The electrochemical reaction of electrochemically reacted hydrogen (H2) with captured carbon dioxide (CO2) offers an alternative route to methanol production. This paper presents a new green poly-generation system consisting of a parabolic trough solar collector (PTC) unit, an organic Rankine cycle (ORC) unit, a CO2 capture unit, an alkaline electrolysis unit, a green methanol synthesis and distillation unit, and a double-effect lithium bromide absorption refrigeration (ARC) unit. The system mainly produced 147.4 kmol/h of methanol at 99.9% purity, 283,500 kmol/h of domestic hot water, and a cooling load of 1341 kW. A total 361.34 MW of thermal energy was supplied to the ORC by the PTC. The alkaline electrolysis unit generated 464.2 kmol/h of H2 and 230.6 kmol/h of oxygen (O2) while providing H2 for methanol synthesis. Thermodynamic and economic analysis of the system was carried out. The energy and exergy efficiency of the whole system could reach 76% and 22.8%, respectively. The internal rate of return (IRR) for the system without subsidies was 11.394%. The analysis for the methanol price showed that the system was economically viable when the methanol price exceedsed$363.34/ton. This new proposed poly-generation system offers more options for efficiently green methanol production.