The next-generation energy economy relies heavily on hydrogen. Handling hydrogen during production, storage, and transportation requires risk mitigation. In this regard, the application of halide-free additives is very crucial. The present study experimentally and theoretically investigates the individual and combined inhibiting effect of propane and propene on hydrogen-air explosions. The experiments are carried out at 298 K and 1 bar, with additives ranging from 0.5 to 5% for the individual and 1–2% each for the combined effect in the 20–50% hydrogen-air mixture. Experimentally, the additive content in the stoichiometric and rich mixture decreases the explosion pressure, maximum pressure rise (MPR) rate, laminar burning velocity (LBV), and flame temperature, while increasing minimum ignition energy. For instance, the addition of 2% propane in a 50% hydrogen-air mixture, reduces the MPR rate by 98%, whereas such an effect is observed with 2.5% propene. Theoretical study shows that 3% equivalent additive augments inhibiting reactions, countering the main flame-promoting reaction R1 (H + O2O + OH) and thereby reducing LBV. Due to its low activation energy, propene consumes the active radicals twice the rate of propane, while propane not only scavenges the active radicals but also promotes oxygen consumption in the prior phase of combustion, weakening flame propagation. Overall, this approach exhibits a significant step forward in harnessing the potential of hydrogen while mitigating the safety risks associated with its use.