Covering: up to the end of 2022 Natural products (NPs) have found uses in medicine, food, cosmetics, materials science, environmental protection, and other fields related to our life. Their beneficial properties along with potential toxicities make the detection and discrimination of NPs crucial for their applications. Owing to the merits of low cost and simple operation, optical sensor arrays, including colorimetric and fluorometric sensor arrays, have been widely applied in the detection of small molecule NPs and discrimination of structurally similar small molecule NPs or complex mixtures of NPs. This review provides a brief introduction to the optical sensor array and focuses on its progress toward the detection and discrimination of NPs. We summarized the design principle of sensor arrays toward various NPs (i.e., saccharides and polyhydroxy compounds, organic acids, flavonoids, organic sulfur compounds, amines, amino acids, and saponins) based on their functional groups and characteristic chemical properties, along with representative examples. Moreover, the challenges and potential directions for further research of optical sensor arrays for NPs are proposed.