<p>Layered organic–inorganic hybrid perovskites exhibit superior ferroelectricity and stability owing to their unique structural configurations. In this work, we investigate the self-powered optoelectronic properties of both single crystals and thin films of a novel layered organic–inorganic hybrid perovskite material—(EATMP)PbBr₄ (EATMP = 2-ethylamino-4-methylpyridinium). The single crystals demonstrate significantly higher photocurrent density than the thin films, attributed to their lower defect density and enhanced carrier mobility. Furthermore, we reveal the critical role of ferroelectric polarization in regulating photocurrent, where switching the polarization direction effectively modulates the magnitude and direction of the photocurrent. Notably, this material can achieve self-powered ultraviolet detection under zero bias, highlighting its potential for optoelectronic applications. This study not only offers new insights into the interplay between ferroelectricity and optoelectronics in hybrid perovskites but also provides valuable guidance for designing high-performance polarization-sensitive photonic devices.</p>