Cationic polymerization of styrene has been achieved using several novel acidic initiators in room temperature ionic liquids (ILs) under mild reaction conditions to obtain polymers of low molecular weight with narrow polydispersity. Both strong protic acids such as bis(trifluoromethanesulfonyl) amide acid (HTFSA) and a moderately weak acid such as bisoxalato phosphorous acid (HBOP) have been studied as initiators. It has been observed that HTFSA initiates the polymerization rapidly even at room temperature and below, as compared to HBOP which produces a slower polymerization requiring elevated temperatures to complete. The relative difference in reactivity of the initiators as compared to the previously described HBOB initiator is discussed in terms of the difference in their proton acidity and the consequential basicity of the anions. The efficiency of different ILs as the reaction solvent is also presented. Cationic polymerization of styrene has been achieved using several novel acidic initiators in room temperature ionic liquids (ILs) under mild reaction conditions to obtain polymers of low molecular weight with narrow polydispersity. Both strong protic acids such as bis (trifluoromethanesulfonyl) amide acid (HTFSA) and has a moderately weak acid such as bisoxalato phosphorous acid (HBOP) have been studied as an initiators. It has been observed that HTFSA initiates the polymerization rapidly even at room temperature and below, as compared to HBOP which produces a slow polymerization of elevated temperatures to complete The relative difference in reactivity of the initiators as compared to the previous described HBOB initiator is discussed in terms of the difference in their proton acidity and the consequential basicity of the anions. The efficiency of different ILs as the reaction solvent is also presented.