We compared the efficiency droop of InGaN multiple-quantum-well (MQW) blue light-emitting diode (LED) structures grown on silicon(111) and c-plane sapphire substrates and analyzed the efficiency droop characteristics using the rate equation model with reduced effective active volume. The efficiency droop of the LED sample on silicon was observed to be reduced considerably compared with that of the identical LED sample on sapphire substrates. When the measured external quantum efficiency was fitted with the rate equation model, the effective active volume of the MQW on silicon was found to be ~1.45 times larger than that of the MQW on sapphire. The lower efficiency droop in the LED on silicon could be attributed to its larger effective active volume compared with the LED on sapphire. The simulation results showed that the effective active volume decreased as the internal electric fields increased, as a result of the reduced overlap of the electron and hole distribution inside the quantum well and the inhomogeneous carrier distribution in the MQWs. The difference in the internal electric field of the MQW between the LED on silicon and sapphire could be a major reason for the difference in the effective active volume, and consequently, the efficiency droop.