Discriminative optical sensors with pattern recognition properties and high-throughput ability have been widely developed as they can distinguish multiple chemically similar analytes. Compared to traditional sensor arrays composed of a series of sensor elements, single-system based discriminative sensors using an array of optical changes at different wavelengths to provide input signals have drawn intensive attention recently. On the one hand, they can provide discrimination ability that is lack in using selective sensors; on the other hand, they can simplify the complex data acquisition process accompanied by multiple-element-based sensor arrays and reduce consumption of sensor samples. This tutorial review gives an overview of the development of single-system based discriminative optical sensors. Different strategies for the construction of single-system based discriminative sensors including dynamic combinatorial libraries, cross-reactive conjugated polymers, DNA G-quadruplex ensembles, combinatorial fluorescent molecular sensors, and fluorophore/surfactant aggregate ensembles are particularly introduced.