The selective separation of CO2 from CH4-containing gases is crucial to produce clean energy gases. In this study, triazole anion-functionalized ionic liquids (TAFILs) were designed by combining low molecular weight cations with triazole anions containing N electronegative site, and further mixed with physical solvents to form physicochemical absorbents. The results indicated that [Cho][Triz]/TMS (80 wt%/20 wt%) not only absorb 0.125 g CO2/g absorbent equal to that of 30 wt% MEA solution at 40 °C and 1 bar, but also have low enthalpy of -35.76 kJ/mol less than half of 30 wt% MEA solution. Simultaneously, superhigh CO2/CH4 selectivity of 191.0 higher than most of reported absorbents is obtained for [Cho][Triz]/TMS solvents. Such great performance of CO2 separation was attributed to relatively weak chemical and physical interaction between CO2 and TAFIL binary absorbents. This study may provide novel promising IL absorbents for CO2 capture applications from clean energy gases.