The process intensification principles of optimizing the driving forces/resistances at every scale and the spatial domain were investigated using a print-assisted technique. The investigation was done by using a LaserJet printer to fabricate structured mixed-matrix membranes for gas separation. The physico-chemical properties of the fabricated membranes were evaluated using FTIR, and XRD. The microstructure of the membrane was evaluated using Scanning Electron Microscope (SEM) and optical microscope. The separation performance was evaluated using constant-pressure gas permeation test. The capability of the membrane to separate a mixture of two gases were tested using CO2 and CH4. The results from optical microscope analysis showed that membrane fabricated using print-assisted method possessed a well-structured morphology which can enhance the predictability of their performance. The gas permeations results showed that the transport mechanism of the membranes changed from Knudsen to molecular sieve as the number of print layers was increased from 0 to 7 layers. Overall, the fabricated membrane showed some potentials for separating CO2/CH4 mixture.