Fuel reactivity is a flexible and feasible method to control combustion, thus reactivity-controlled compression ignition (RCCI) has the potential to achieve lower emissions and higher thermal efficiency. However, the exergy loss during combustion hinders the further exergy-work transform, which limits the thermal efficiency further improvement. The present work focuses on the relationship between fuel reactivity and exergy which contains exergy loss (EL) and thermomechanical exergy (Exthermo due to the temperature and pressure imbalance between system and reference state). By varying the reactivity of primary reference fuels (PRFs) with different initial boundary conditions, it is found that different PRFs could not reduce EL and change Exthermo under same condition but could change the exergy loss rate as well as the EL structure by influencing low-temperature combustion. In terms of boundary conditions, both high temperature and lean mixture could improve Exthermo but with different mechanism: high temperature saving EL into Exthermo, lean mixture recovering incomplete combustion exergy (Exincom) into Exthermo. By contrast, equivalence ratio more easily affects EL and Exthermo. In three-dimensional situation, it is found that decreasing reactivity of PRFs leads more in-cylinder area below equivalence ratio 1.0 which benefits for the Exthermo improvement, but it would cause Exthermo structure mutation which is unfriendly for the smooth output of work near top dead center. The conversion of fuel exergy to final useful work is indirect, and there exist two sub-processes: fuel exergy to thermomechanical exergy then thermomechanical exergy to useful work. The final exergy-work transform efficiency is influenced by both processes. Therefore, using low reactivity fuel as PRF90 in engine is favor of the exergy from fuel transforming into Exthermo by more lean mixture, adopting high reactivity fuel as PRF0 is favor of the Exthermo sequential structure which is benefit for the combustion control and useful work extract near top dead center. Therefore, there is potential to further improve the thermal efficiency by using a dual-fuel combination, with the low reactivity fuel creating a low equivalence ratio region to improve the thermomechanical exergy, and the high reactivity fuel achieving precise phase control during the combustion.