Carboxylated carbon nanotubes (C or cCNTs) were incorporated in polyethersulfone hollow fiber membranes (P HFMs) to improve the gas separation performance, i.e., pure gas permeability and ideal gas selectivity. The developed CP HFMs showed the remarkable improvement in thermal stability and mechanical strength as compared to that of the pristine P HFMs. The pure gas permeability of CO2, CH4, O2, and N2 gases for the HFMs were measured at 3 bar feed pressure and room temperature. It was observed that the presence of cCNTs in HFMs significantly improved the CO2 and O2 permeability for CP HFMs by 10.8-and 11.7- fold, respectively, as compared to that measured for P HFMs. Furthermore, the ideal gas selectivity for CO2/CH4, O2/N2, and CO2/N2 gas pairs for CP HFMs was also remarkably enhanced by almost 8.6-, 10.7-and 9.9-times, respectively, as compared to that measured for P HFMs. CP HFMs exhibited gas separation performance better than or comparable to that of the literature-reported CNTs-based membranes. Remarkably, the gas separation performance of CP HFMs crossed Robeson’s 2008 upper bound curve for O2/N2 gas-pair and was almost closer to the upper bound curves drawn by Robeson in 2008 for CO2/CH4 and CO2/N2 gas pairs. The improved separation performance can be attributed to the presence of cCNTs in HFMs. Thus, the results obtained in this study clearly showed that the CP HFMs can potentially be used as a membrane material for the industrially relevant gas separations.