Developments in industrial applications inevitably accelerate the discharge of enormous substances into the environment, whereas multi-component mixtures commonly cause joint toxicity which is distinct from the simple sum of independent effect. Thus, ecotoxicological assessment, by luminescent bioassays has recently brought increasing attention to overcome the environmental risks. Based on the above viewpoint, this review included a brief introduction to the occurrence and characteristics of toxic bioassay based on the luminescent bacteria. In order to assess the environmental risk of mixtures, a series of models for the prediction of the joint effect of multi-component mixtures have been summarized and discussed in-depth. Among them, Quantitative Structure-Activity Relationship (QSAR) method which was widely applied in silico has been described in detail. Furthermore, the reported potential mechanisms of joint toxicity on the luminescent bacteria were also overviewed, including the Trojan-horse type mechanism, funnel hypothesis, and fishing hypothesis. The future perspectives toward the development and application of toxicity assessment based on luminescent bacteria were proposed.