Perenniality is one of the important topics in rice breeding which is generally accompanied by complex physiobiochemical processes. To understand the metabolic characteristics of perennial rice, in the present study, gas chromatography-mass spectrometry and enzyme-linked immunosorbent assays were used to profile the distribution patterns of 33 primary metabolites and hormones [indole-3-acetic acid (IAA) and zeatin riboside (ZR)] of annual (RD23) and perennial (Oryza longistaminata and the line AA with RD23 genetic background) rice genotypes. Results showed that both metabolites and hormones have distinct genotype and organ distribution patterns, and considerable variations were observed between the metabolites in stem bases of perennial and annual rice. Most of the metabolites, including sugars, organic acids, and amino acids, significantly accumulated in the stem bases of perennial rice by decreasing the level in roots and leaves. Fifteen metabolites consistently accumulated significantly in the stem bases of both perennial genotypes. Additionally, the organ-level IAA content and IAA/ZR ratio in the two perennials were considerably higher than those in RD23. The present study indicated that the significant accumulation of the metabolites at stem base and the higher IAA/ZR ratio are involved in the regulatory metabolism for rhizome development.