A process strategy to aid in optimal enzymatic hydrolysis through the addition of polyethylene glycol (PEG6000) was tested for separate hydrolysis and fermentation (SHF) and simultaneous saccharification and fermentation (SSF). Pretreated wheat straw at 30% solids (w/w) loading was enzymatically hydrolyzed with 0, 0.5, 1, 1.5, 2 and 2.5% of PEG6000 through SHF and SSF. During SHF, bioethanol concentration of 107.5 g/L (2.5% PEG6000) was achieved. SSF ethanol concentration were about 113 g/L at 1.5% PEG6000 addition. A technoeconomic feasibility showed a return on investment (ROI) of 8.13% using 0.5% PEG6000 for SHF (96 h) and 12.25% ROI for SSF control (72 h). Life cycle assessment for the various scenarios indicated higher environmental gains for best cases of SSF over SHF. The study shows the SSF approach (0% PEG6000; 72 h) facilitates higher process efficiencies; technoeconomic gains and high environmental sustainability for future scale-up and commercial realization.