Molecular solar thermal fuels (MOSTs), especially azobenzene-based MOSTs (Azo-MOSTs), have been considered as ideal energy-storage and conversion systems in outer or confined space because of their “closed loop” properties. However, there are two main obstacles existing in practical applications of Azo-MOSTs: the solvent-assistant charging process and the high molar extinction coefficient of chromophores, which are both closely related to the π–π stacking. Here, we report one efficient strategy to improve the energy density by introducing a supramolecular “cation−π” interaction into one phase-changeable Azo-MOST system. The energy density is increased by 24.7% (from 164.3 to 204.9 J/g) in Azo-MOST with a small loading amount of cation (2.0 mol %). Upon light triggering, the cation−π-enhanced Azo-MOST demonstrates one gravimetric energy density of about 56.9 W h/kg and a temperature increase of 8 °C in ambient conditions. Then the enhanced mechanism is revealed in both molecular and crystalline scales. This work demonstrates the huge potential of supramolecular interaction in the development of Azo-MOST systems, which could not only provide a universal method for enhancing the energy density of solar energy storage but also balance the conflicts between molecular design and the condensed state for phase-changeable materials.