The performance of electrode material is correlated with the choice of electrolyte, however, how the solvation has significant impact on electrochemical behavior is underdeveloped. Herein, N‐heteropentacenequinone (TAPQ) is investigated to reveal the solvation effect on the performance of sodium‐ion batteries in different electrolyte environment. TAPQ cycled in diglyme‐based electrolyte exhibits superior electrochemical performance, but experiences a rapid capacity fading in carbonate‐based electrolyte. The function of solvation effect is mainly embodied in two aspects: one is the stabilization of anion intermediate via the compatibility of electrode and electrolyte, the other is the interfacial electrochemical characteristics influenced by solvation sheath structure. By revealing the failure mechanism, this work presents an avenue for better understanding electrochemical behavior and enhancing performance from the angle of solvation effect. N‐heteropentacenequinone (TAPQ) is studied as electrode material to investigate the solvation effect in different sodium‐ion battery electrolytes. By revealing the failure mechanism of TAPQ in carbonate‐based electrolytes, we discuss how the solvation effect influences interfacial electrochemical characteristics and attributed the electrolyte compatibility to the stabilization effect of reaction intermediate via solvation effect.