A novel microwave assisted surfactant pretreatment strategy was evaluated for the production of bioethanol and biopolymer from chili post-harvest residue. Among the various surfactants screened microwave assisted Tween - 20 pretreatment was found to be more effective. Various process parameters affecting pretreatment were optimized by adopting a Taguchi design. The optimum conditions of pretreatment were surfactant concentration of 4% w/w, MW pretreatment time for 1 min, MW power of 550W, biomass loading of 5% w/w and pretreatment time for 45 min. Under optimized conditions 0. 316g/g of reducing sugar per g of dry biomass (g/g) was observed. The hydrolyzate is devoid of major fermentation inhibitors like furfural, 5-hydroxymethylfurfural and organic acids like citric acid, propionic acid, succinic acid and formic acid. Fermentation of the non-detoxified hydrolyzate yielded 1.66% of ethanol and 67.85% of PHB.