This study was conducted to prepare a mixed matrix membrane (MMM) and to test the performance of the prepared MMM for CO2 and CH4 gas separation. MMM containing polyethersulfone (PES) and multi-walled carbon nanotubes (MWCNTs) was prepared by a dry-wet phase inversion technique using a pneumatically-controlled membrane casting machine. The surface modification was performed on MWCNTs in order to enhance the selectivity of CO2/CH4. The surface modification of MWCNTs using chemical and physical approaches has been adopted. Mixed acid (HNO3/H2SO4) and β-CD were used for chemical and physical approaches, respectively. Effects of surface modification on MWCNTs/PES MMM were investigated. MWCNTs/PES MMMs were characterised using scanning electron microscopy (SEM), the Fourier Transform Infrared (FT-IR) spectroscopy and pure gas permeation test. The permeability and selectivity, which are the parameters describing membrane performance were calculated via the data obtained from pure gas permeation test with the feed pressure difference from 3 to 7 bars. In this study, surface modified MWCNTs/PES MMM using mixed acid and β-CD has successfully enhanced the CO2/CH4 selectivity by 40.6% compared to that of neat PES.