We investigated new anodic coloring materials that are used as ion storage layers in complementary energy storage electrochromic devices (ESECDs) to enhance their electrochromic storage performance. In this study, we fabricated counter electrodes (ion storage layers) using IrO2 doping NiO (Ir: NiO) film through cathodic arc plasma (CAP) with varying surface charge capacities. We investigated the influence of MoO3-doped WO3 (Mo: WO3) film by various Ar/O2 gas flow ratios (1/4, 1/5, and 1/6). The ESECDs used in the demonstration were 10×10 cm2 in size. They achieved optical transmittance modulation of Ir: NiO- ESECDs (glass/ITO/ Mo: WO3/gel-polymer electrolytes/ Ir: NiO /ITO/glass), ΔT=53.3% (from Tbleaching (66.6%) to Tcoloration (13.1%)). The ESECDs had a quick coloration time of 3.58 seconds, a rapid bleaching time of 1.24 seconds, and high cycling durability. It remained at 45% transmittance modulation even after 3000 cycles. New anodic materials can provide an alternative to traditional active materials for bi-functional electrochromic batteries.