The engine performance has been improved by modifying the combustion chamber shape of the diesel engine for dual-fuel operation with liquid fuel and producer gas (PG). The combined effect of gaseous fuel from redgram stalk and combustion chamber type on the emission and performance of blended-fuel of diesel and HOME biodiesel–PG has been investigated. In this experimental study, four varieties of combustion chambers hemispherical (HCC), low swirl (LSCC), dual swirl (DSCC), and toroidal re-entrant (TRCC) were analyzed comprehensively. The results presented that the TRCC configuration with a given nozzle geometry has 9% improved brake thermal efficiency (BTE) and 10.4% lower exhaust gas temperature (EGT). The smoke, unburnt hydrocarbon (UBHC), and carbon monoxide (CO) decreased by 10–40%, but a 9% increase in nitrogen oxides (NOX) emission levels was observed with TRCC. The delay period and combustion period were decreased by 5% and 7%. The fuel replacement of about 71% for the diesel–PG combination with HCC and 68% for the HOME–PG combination with TRCC was achieved.