<div>A numerical investigation has been performed in the current work on reactivity-controlled compression ignition (RCCI), a low-temperature combustion (LTC) strategy that is beneficial for achieving lower oxides of nitrogen (NO<sub>x</sub>) and soot emission. A light-duty diesel engine was modified to run in RCCI mode. Experimental data were acquired using diesel as HRF (high-reactivity fuel) and gasoline as LRF (low reactivity fuel) to check the accuracy and fidelity of predicted results. Blends of ethanol and gasoline with DTBP (di-tert-butyl peroxide) addition in a small fraction on an energy basis were used in numerical simulations to promote ignitability and reactivity enhancement of PFI charge. Achieving stable, smooth, and gradual combustion in RCCI is challenging at low loads, especially in light-duty engines, due to misfiring and poor combustion stability. DTBP is known for enhancing cetane number and accelerating combustion, and it is mixed in a PFI blend to avoid combustion deterioration. The factors governing reactivity stratification to achieve optimal combustion phasing were investigated in the present study. DTBP decomposition and its low-temperature oxidation chemistry were found to be responsible for affecting combustion phasing, heat release patterns, and emission trends. DTBP additive and different in-cylinder strategies were applied and studied to reduce unburned emissions. Adopting a multiple injection approach utilizing dual-pulse assisted in reducing HC and CO levels. It enhances combustion quality by providing adequate control over combustion phasing. Altering operating parameters like intake temperatures reduced HC, CO, and soot emissions by 97.6%, 57.6%, and 52.8%, respectively, compared to baseline gasoline/diesel RCCI data. Optimizing the injection timings of the first and second pulse helps achieve optimal combustion phasing and a 72.95% reduction in NO<sub>x</sub> emissions. The higher injection pressure of DI helped lower the CO and soot emissions by 53.33% and 51.84%, respectively.</div>