Combustible fuels like methyl pentanoate (MPe) could cause accidental explosions and fire. Therefore, MPe explosion characteristics have to be well characterized and understood for its safe and reliable use in industries and combustion devices. Considering this, MPe’s explosion pressure, maximum explosion pressure, rate of pressure rise, maximum rate of pressure rise, heat release rate, etc., were investigated in this study at the initial conditions of 1, 2, and 4 bar and 423 K, 453 K, and 483 K using the equivalence ratios of 0.7–1.4. The maximum explosion pressures and maximum rate of pressure rise of MPe increased as the initial pressures increased but the maximum rate of pressure rise was insignificantly affected by the initial temperature. The explosion duration decreased with a decrease in the initial pressure. The maximum heat release rate and deflagration index increased with increasing initial pressure. The MPe maximum deflagration index was 224.8 bar•m/s, which occurred at a higher initial pressure and fuel-rich mixture. Therefore, the explosion severity of MPe was enhanced at higher initial pressures and fuel-rich mixtures. Moreover, the flame cellularity study showed that MPe unstable flame crack length and cell number were more affected by increments in the initial pressure and equivalence ratio. Therefore, flame instability and cellularity would significantly influence explosion severity at higher pressures and equivalence ratios. This study’s findings provide first-hand data that could be used to further investigate and characterize MPe’s explosion risk.