With the development of gut microbiota-specific interventions for mental disorders, the interactions between plant polysaccharides and microbiota in the intestinal and their consequent effects are becoming increasingly important. In this review, we discussed the role of plant polysaccharides in improving various mental disorders via the microbiota–gut–brain axis. The chemical and structural characteristics and metabolites of these plant polysaccharides were summarised. Plant polysaccharides and their metabolites have great potential for reshaping gut microbiota profiles through gut microbiota-dependent fermentation. Along the microbiota–gut–brain axis, the consequent pharmacological processes that lead to the elimination of the symptoms of mental disorders include 1) regulation of the central monoamine neurotransmitters, amino acid transmitters and cholinergic signalling system; 2) alleviation of central and peripheral inflammation mainly through the NLRP3/NF-κB-related signalling pathway; 3) inhibition of neuronal apoptosis; and 4) enhancement of antioxidant activities. According to this review, monosaccharide glucose and structure -4-α-Glcp-(1→ are the most potent compositions of the most reported plant polysaccharides. However, the causal structure-activity relationship remains to be extensively explored. Moreover, mechanistic elucidation, safety verification, and additional rigorous human studies are expected to advance plant polysaccharide-based product development targeting the microbiota–gut–brain axis for people with mental disorders.