A series of binary-salt electrolytes of KPF6/KN(SO2F)2 (KFSA) in carbonate ester solvents have been developed for high-voltage K-ion batteries by clarifying the effect of salt ratio and different solvents on the physical properties of the electrolyte solutions and electrochemical performance of K-ion batteries. The KPF6/KFSA carbonate ester solutions, such as KPF6/KFSA ethylene carbonate (EC)/diethyl carbonate (DEC), exhibit higher ionic conductivity than single-salt KPF6 one, and higher KFSA content results in higher ionic conductivity. The KPF6-rich binary-salt electrolytes with KPF6/KFSA ratios of ≥3 (mol/mol) provide enough oxidation stability and passivation against Al corrosion at 4.6 V over 100 h, ensuring reversible operation of a 4 V class positive electrode, K2Mn[Fe(CN)6] in half-cell. Graphite negative electrodes exhibit higher Coulombic efficiency and better rate performance in 0.75 mol kg-1 K(PF6)0.9(FSA)0.1/EC/DEC and 1 mol kg-1 K(PF6)0.75(FSA)0.25/EC/DEC electrolytes than those in the KPF6 one. Surface analysis by hard X-ray photoelectron spectroscopy reveals that the decomposition product of N(SO2F)2- anion contributes to stabilizing solid electrolyte interphase on a graphite electrode. From comparing different solvents of EC/DEC, EC/ethyl methyl carbonate, and EC/propylene carbonate (PC), the K2Mn[Fe(CN)6] electrode demonstrates the highest Coulombic efficiency in the EC/PC binary electrolyte, while graphite electrodes exhibit no significant difference. Based on the half-cell tests, we successfully achieve the 3.6 V class full cell of graphite|K(PF6)0.75(FSA)0.25/EC/PC|K2Mn[Fe(CN)6] showing excellent cyclability over 500 cycles, which is far superior to that of the conventional KPF6/EC/DEC electrolyte cell.