Solubility parameters are effective factors for controlling membrane preparation based on hydrophilic/hydrophobic polymers. Hansen solubility parameters (HSPs) of a polysulfone/polyethylene glycol (PSU/PEG) in increasing PEG molecular weights and binary coagulation bath of solvent/non-solvent mixtures are investigated. The results revealed that with increased PEG molecular weight in the casting solution, the relative energy difference (RED) of the solution increases, and subsequently its instability increases too. On the other hand, by increasing the solvent in the coagulation bath, RED decreases. Findings demonstrated that by increasing PEG molecular weight to 15,000 g/mol and increasing solvent to 60 wt% in the coagulation bath, an interconnected sponge-like structure with maximum mean pore size (120 nm) was achieved. With increased PEG molecular weight, membrane morphology tended toward to a sponge-like structure due to delayed demixing in the phase inversion stage. Furthermore, pure water permeability and rejection capability of membranes exhibited that with increasing RED of casting solution and reducing RED of coagulation bath, the highest permeability (2199 L/m2h and the lowest rejection capability (33%) of the membrane were attained. This study confirmed that, for the PSU/PEG system, by controlling the solubility parameters, RED value of casting solution and coagulation bath, membrane characteristics can be controlled.