Polyethylene glycol (PEG)-based polyurethane/polyacrylonitrile (PU/PAN, 50/50) semi-interpenetrating polymer network (SIPN) membrane has been studied from sorption/desorption cycles and diffusion behaviour with substituted aromatic probe molecules at 20, 40 and 60 °C. Sorption/desorption cycles have been repeated to evaluate polymer–solvent interaction. Organic solvents taken up or given out by IPN are measured periodically till equilibrium. Using these data, sorption ( S), diffusion ( D) and permeation ( P) coefficients have been calculated from Fick's equation. Sorption data is correlated with solubility parameter of solvents and polymer. It was found that solvents of comparable solubility parameter with IPN interact more and thus there is an increase in sorption. Molecular mass between cross-link has been calculated using Flory Rehner equation. The cross-link density and degree of cross-linking of the membrane is calculated. From the temperature dependence of sorption and diffusion coefficients, the Arrhenius activation parameters like activation energy for diffusion ( E D ) and permeation ( E P ) processes have been calculated. Furthermore, the sorption results have been interpreted in terms of thermodynamic parameters such as change in enthalpy (Δ H) and entropy (Δ S). Concentration profiles of penetrants at different penetration depths in the polymer sample at different time intervals have also been calculated theoretically from a solution of Fick's equation under appropriate initial boundary conditions.