The influence of electrolyte composition (Zn(CF3SO3)2 vs. ZnSO4) on the electrochemical performance of VO2/PPy cathode for aqueous zinc-ion batteries was systematically investigated. The electrochemical performance of VO2/PPy composite in Zn(CF3SO3)2 is significantly superior compared to that in ZnSO4. After 250 cycles, the triflate electrolyte enabled a capacity retention of 60% (maximum 306.3 mAh·g−1), while the sulfate system retained only 24% of its initial capacity. The results obtained demonstrate that the combination of VO2/PPy cathode with a zinc triflate electrolyte provides superior rate capability, cycling stability, and charge-transfer kinetics compared to the sulfate-based system.