Utilizing phosphine (PH3) tail gas as starting feedstock, a series of novel mono-and bifucntionalphosphonium compounds (P+(CH2CH2CN)3RX , X= Br, I) was prepaed by a sustainable preparation route. The newly prepared phosphonium halides show high thermal stability and their degradationtemperature are far higher than that of CO2 chemicalfixation. The mono-fucntional phosphoniumsalts combinate with ZnBr2 to form an efficient Lewis acid/base type catalytic system for CO2 chemicalfixation and the bifucntional phosphonium salts alone shows same catalytic effects. The effects oftemperature, CO2 pressure, composition of the catalytic system on coupling reaction of CO2 withepoxides are investigated to evaluate the catalytic performance. The results illustrate that 96.7% cyclicCarbonate yield can be obtained in presence of ZnBr2/P+(CH2CH2CN)3C4H9Br (molar ratio = 1:10) under120 C, 1.5MPa of CO2 pressure in solvent-free condition, menawhile bifuntional phiospohonium salt Br-P+(CH2CH2CN)3C2H4COOH alone shows better catalytic perofromance.