The development of organic‐based optoelectronic technologies for the indoor Internet of Things market, which relies on ambient energy sources, has increased, with organic photovoltaics (OPVs) and photodetectors (OPDs) considered promising candidates for sustainable indoor electronic devices. However, the manufacturing processes of standalone OPVs and OPDs can be complex and costly, resulting in high production costs and limited scalability, thus limiting their use in a wide range of indoor applications. This study uses a multi‐component photoactive structure to develop a self‐powering dual‐functional sensory device with effective energy harvesting and sensing capabilities. The optimized device demonstrates improved free‐charge generation yield by quantifying charge carrier dynamics, with a high output power density of over 81 and 76 µW cm−2 for rigid and flexible OPVs under indoor conditions (LED 1000 lx (5200 K)). Furthermore, a single‐pixel image sensor is demonstrated as a feasible prototype for practical indoor operating in commercial settings by leveraging the excellent OPD performance with a linear dynamic range of over 130 dB in photovoltaic mode (no external bias). This apparatus with high‐performance OPV‐OPD characteristics provides a roadmap for further exploration of the potential, which can lead to synergistic effects for practical multifunctional applications in the real world by their mutual relevance. The dual‐functional sensory device exhibits efficient molecular packing and excellent free‐charge generation yield by quantifying charge‐carrier dynamics, resulting in a high output power density of over 94 µW cm−2 for OPVs, under dim indoor illumination (LED 1000 lx). Moreover, it demonstrates the feasibility of the proposed device by developing a single‐pixel image sensor for practical indoor operation in commercial settings.