This study investigates the impact of modifying a conventional compression ignition (CI) engine by inducting pentanol in inlet manifold and injecting graphene-blended tamanu biodiesel into the cylinder. These modifications significantly enhance ignition quality and expand operational capabilities within the premixed charge compression ignition (PCCI) engine. The use of graphene-enhanced biodiesel in PCCI mode demonstrates potential for improved combustion efficiency and emission reduction. Dispersed graphene nanoparticles in tamanu biodiesel notably improve brake thermal efficiency due to their increased surface area, which enhances fuel-air mixing. Graphene-suspended biodiesel at a concentration of 100 ppm in PCCI mode results in an 11.5 % peak pressure rise and an 8.4 % rise in heat release rate with respect to pure biodiesel in CI mode. This nano-suspension biodiesel also shows significant thermal efficiency improvements, with an 8.20 % increase and a 22.08 % reduction in fuel consumption with respect to neat biodiesel in CI mode. The combination of pentanol and graphene-blended tamanu biodiesel improves combustion quality, yielding a 13 % reduction in carbon monoxide emissions, a 34.67 % reduction in hydrocarbon emissions, a notable 65.84 % lower in nitrogen oxide, and a 33.91 % reduction in smoke with respect to neat tamanu biodiesel in CI mode of operation.