This review critically examines photoresponsive supercapacitors based on TiO₂/graphene hybrids, with a particular focus on their emerging dual role as energy-storage devices and environmental sensors. We first provide a concise overview of the electronic structure of TiO₂ and the key attributes of graphene and related nanocarbons that enable efficient charge separation, transport, and interfacial engineering. We then summarize and compare reported device architectures and electrode designs, highlighting how morphology, graphene integration strategies, and illumination conditions govern specific capacitance, cycling stability, rate capability, and light-induced enhancement in performance. Particular attention is given to the underlying mechanisms of photo-induced capacitance enhancement—including photocarrier generation, interfacial polarization, and photodoping—and to how these processes can be exploited to embed sensing functionality in working supercapacitors. We review representative studies in which TiO₂/graphene systems operate as capacitive sensors for humidity, gases, and volatile organic compounds, emphasizing quantitative figures of merit such as sensitivity, response/recovery times, and stability under repeated cycling. Finally, we outline current challenges in materials integration, device reliability, and benchmarking, and propose future research directions toward scalable, multifunctional TiO₂/graphene platforms for self-powered and environmentally aware electronics. This work is intended as a state-of-the-art summary and critical guide for researchers developing next-generation photoresponsive supercapacitors with integrated sensing capability.

The integration of energy storage and environmental sensing functions into a single device represents a critical step toward the development of autonomous smart systems. In this work, we report the design and fabrication of photoresponsive supercapacitors based on TiO₂/graphene hybrid electrodes that simultaneously deliver enhanced energy storage performance and environmental monitoring capabilities. The nanocomposite electrodes are prepared via a scalable sol-gel and hydrothermal route, followed by mild thermal treatment to optimize interface interactions and photoactivity. Under UV and visible light illumination, the devices exhibit a significant increase in specific capacitance, up to 35% enhancement, due to improved charge separation and interfacial polarization effects. Moreover, the same hybrid materials demonstrate sensitivity to volatile organic compounds (VOCs) and humidity, enabling their use as dual-function components in next-generation smart electronics. The synergistic combination of light-driven capacitive enhancement and real-time environmental response highlights the potential of these hybrid systems for self-powered, multifunctional platforms in wearable and distributed sensor networks.