In the pursuit of sustainable technology, the synthesis of a novel biopolymer, C‐pBPV, through the polymerization of carboxymethyl cellulose sodium salt (CMC‐Na) and viologen (BPV), with ammonium persulfate as an initiator is presented. This groundbreaking process not only promises an eco‐friendly approach but also opens avenues for advanced applications in electrochromic devices (ECDs), particularly in smart windows, displays, and beyond. Departing from conventional multi‐layered approaches, the study underscores the significance of a single‐layer material. C‐pBPV serves both as an electro‐chrome and an electrolyte, making it a compelling material for ECDs. It is used to create a gel‐based electrochromic device G1 with exceptional bistable properties. Following, a systematically controllable device, G2 is accomplished, to enhance color‐switching capabilities by adding vitamin C as an electron mediator. Both devices exhibited outstanding electrochromic properties, showcasing dual‐band absorption in the Vis‐NIR region, with color transitions from transparency to a striking purple state at low voltages. Embracing an all‐in‐one layer configuration, this study set the stage for next‐generation smart windows that not only regulate solar light for energy conservation but also pioneer a more compact, user‐friendly design, prioritizing visual comfort, sustainability, and a tailored user experience.