Flexoelectricity, an intrinsic property observed in materials under nonuniform deformation, entails a coupling between polarization and strain gradients. Recent catalyst advancements have reignited interest in flexoelectricity, particularly at the nanoscale, where pronounced strain gradients promote robust flexoelectric effects. This paper comprehensively examines flexoelectricity, encompassing methodologies for precise measurement, elucidating its distinctions from related phenomena, and exploring its potential applications in augmenting catalytic properties. So far, the greatest potentials are based on lead strontium titanate (PST) and other metallic titanates such as titania (TiO2), strontium titanate (STO), barium strontium titanate (BST) sulfates (MoS2, ZnS)and halide perovskites (with archetype XPbI3). This review explores the promise of flexoelectric properties in addressing material and photocatalytic challenges, such as charge carrier recombination and ineffective surface charge separation. Additionally, it sheds light on the synergy with emerging paradigms like photo-flexo catalysis and synergistic flexo-piezo catalysis, specifically focusing on selective chemical transformations like green hydrogen production. Current limitations related to the usage of photoflexoelectricity for photocatalysis are mostly the stability of the used substance (susceptibility to photodegradation) or the voltage values, which represent the inferior potential for specific practical applications. This work underscores the indispensable role of flexoelectricity in catalysisand its capacity to steer future researchand technological advancement.