This chapter explores the advancements and current state of asymmetric synthesis in bulk water, highlighting its pivotal role in sustainable chemistry. Advanced small molecular catalysts, including chiral metal complexes and organocatalysts, are showcased, underscoring the versatility of synthetic strategies employed. Focusing on crucial catalytic activation mechanisms, asymmetric reactions in water are categorized into four main types: metal (Lewis acid) catalysis, Lewis base organocatalysis, Brønsted acid, and Brønsted base organocatalysis. The chapter presents significant progress in asymmetric reduction, oxidation, and various bond formation reactions, demonstrating how water can enhance selectivity and reactivity.