Aurbach et al. [5] indicated that calcium deposition was impossible in organic solutions at room temperature. Molten salt cells were demonstrated to exhibit good reversibility at high operating temperature (550-700 °C), [6] which is difficult to meet with the mainstream applications operated under room temperature. Palacín et al. [3a] achieved the deposition of calcium at 75-100 °C and proved its reversibility for over 30 cycles. Recently, using Ca(BH 4 ) 2 in tetrahydrofuran as electrolyte, Ca ions were realized plating and stripping at room temperature for 50 cycles. [7] Up till now, because of the lack of an appropriate combination of suitable electrode materials and electrolytes, [8] it is difficult to construct calcium-based energy storage devices based on the conventional rocking-chairtype mechanism.Multiion reaction mechanism is a possible approach to break Ca-technology barrier, in which anions and cations react with cathode and anode, respectively, during charge process (Figure 1). In general, supercapacitors (SCs) exhibit superior rate and cycling properties [9] and dual-ion batteries (DIBs) have displayed high capacity and working voltage. [10] Meanwhile, SCs have to stop storing charge when the potential of either electrode reaches the threshold of electrolyte, [11] which prevents SCs from fully utilizing the voltage window of electrolyte, resulting in relatively low capacity and voltage. As for DIBs, the anion intercalation/deintercalation on cathode side will destabilize the structure for the large radius of anions (TFSI − , PF − 6 , etc.), thus degrading the cycling and rate performance. [12] Recently, Tang et al. developed a reversible calcium-based DIB at room-temperature, [13] but the cycling stability (350 cycles) and rate performance (the capacity remained 55% when the current density increased from 0.1 to 0.4 A g −1 ) were far from practical applications.Herein, we reported a novel calcium-ion hybrid energy storage device (Ca-HSC) at room temperature via combining the features of SCs and DIBs (Figure 1c), in which capacitor component cathode and battery component anode served as a complementary to each other while maintaining their unique advantages. [14] In detail, the stable and low anodic potential of this device caused by Faradaic reaction allowed the cathode potential to be tested up until the upper limit of electrolyte, enabling large capacity and high voltage. Meanwhile, the non-Faradaic reaction at the cathode brought fast kinetics performance and long cycling life. After optimization, this Ca-based Ca-ion based devices are promising candidates for next-generation energy storage with high performance and low cost, thanks to its multielectrons, superior kinetics, as well as abundance (2500 times lithium). Because of the lack of an appropriate combination of suitable electrode materials and electrolytes, it is unsuccessful to attain a satisfactory performance on complete Ca-ion energy storage devices. Here, the multiion reaction strategy is defined to construct a complete Ca-ion ener...