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β-agonists are a class of synthetic phenylethanolamine compounds that were originally designed to reduce asthma and chronic obstructive pulmonary disease. They remain widely used but unfortunately, misuse in animal farming and sports activities due to their huge medical and economic benefits. As a result, they have been found in a variety of matrices and subsequently end up in multiple water bodies in the environment. However, their environmental occurrence and fates are only evaluated on an occasional basis as they happen at a very trace level. The development of appropriate analytical procedures is critical in providing reliable data related to their occurrence and concentrations in various water bodies. Coupling high-performance liquid chromatography and mass spectrometry have been the most extensively used approach for great sensitivity and high selectivity for their determination in the environment. Sample preparation is important for obtaining lower detection limits, and the online solid-phase extraction has been comprehensively used considering the physicochemical properties of β-agonists. This review presented the systematic development of the preceding research on β-agonist detection approaches published between 1985-2020, emphasizing their analysis, resolution in environmental waters, and highlighting the significant scientific approach from the existing analytical techniques suitable for their ultra-trace determination.