Abstract: This article reviewed the existing forms，results of spectroscopic study and influencing factors of polyborate anions in borate solutions.Besides the commonB(OH)↓4\〗-，B(OH)↓3，B↓3O↓3(OH)↓4\〗-，B↓4O↓5(OH)↓4\〗↑2-，B↓5O↓6(OH)↓4\〗- and B↓6O↓7(OH)↓6\〗↑2-，there are also other existing forms of polyborate anion，such as B↓2O(OH)↓6\〗↑2- and B↓3O↓3(OH)↓5\〗↑2- etc.and all these groups interact each other.The existing forms and interaction of polyborate anions were further illustrated by the study results of FT-IR and Raman spectrum.The existing forms and interaction of each group are relative to the concentration of total boron，pH，metallic cations，temperature and hydrothermal condition，and are mainly dependent on the concentration of total boron and pH.If the concentration of total boron is higher and the pH is lower，there are more high polymerized borate anions；if not，there are more low polymerized borate anions.