The separation ability of bis(triethoxysilyl)ethane (BTESE) membranes for hydrogen (H2) purification from hydrogen (H2)/toluene (TOL) gas mixtures after a methylcyclohexane (MCH) dehydrogenation process was investigated via one-stage and two-stage membrane processes. This study revealed that BTESE membranes of varied pore sizes (0.4, 0.5, and 0.7 nm) in a one-stage configuration can manage to achieve a H2 purity ~99.9%. However, the TOL concentrations fell within a wide range, ranging from 280 to 5441 ppm. A primary goal of this research was to lower the TOL concentration in the permeate stream below 200 ppm. Hence, by applying the two-stage membrane, it was demonstrated that the TOL concentration in the permeate stream could be lowered below 200 ppm.