Crystalline coordination networks with an infinite extended framework, also known as coordination polymers (CPs) or metal-organic frameworks (MOFs), have attracted significant attention owing to their tremendous performance in an extensive range of applications. The unique structural features and high stability of coordination networks are responsible for their utilization and potential in diverse fields especially in the area of sensing using luminescent CPs/MOFs. The recognition of toxic oxo-anions present in water is a crucial and first step towards environmental remediation, mainly in the case of water pollution. Accordingly, the utilization of luminescent coordination networks has received significant interest, particularly for the recognition of various toxic oxo-anions, which are considered a threat to aquatic life and the environment. In this frontier article, we summarize recent reports on luminescent CPs/MOFs, their utilization for the sensing of oxo-anions and the chemistry of the interaction of oxo-anions with CPs/MOFs, which is responsible for tuning their optical signals.