As a leading Pb-free perovskite material (ABO3-type), potassium sodium niobate (K,Na)NbO3 (KNN)-based ferroelectrics/piezoelectrics have been widely used in electronics, energy conversion, and storage due to their exceptional ability to interconvert mechanical and electrical energies. Beyond traditional applications, the piezoelectric potential generated by mechanical strain or stress modifies their energy band structures and facilitates charge carrier separation and transport, drawing increasing attention in emerging fields such as piezocatalysis and photo-piezocatalysis. With excellent piezoelectric properties, chemical/thermal stability, and strain-tuning capability, KNN-based materials show great promise for high-performance piezocatalytic applications. Coupling KNN with semiconductors exhibiting strong optical absorption to form heterojunctions further boosts performance by suppressing electron-hole recombination and promoting directed charge transfer, which is crucial for photo-piezocatalysis. The flexibility of KNN's perovskite structures also allows for modifications in chemical composition and crystal structure, enabling diverse design strategies such as defect engineering, phase boundary engineering, morphology control, and heterojunction formation. This review comprehensively explores the recent advancements in KNN-based piezocatalysis and photo-piezocatalysis, starting with an overview of their crystal structures and intrinsic properties. It then explores the role of piezoelectric potential in charge carrier dynamics and catalytic activity, followed by strategic design approaches to optimize efficiency in environmental remediation and energy conversion. Finally, the review addresses current challenges and future research directions aimed at advancing sustainable solutions using KNN-based materials in these applications.