Different morphologies of calcium borate 2CaO·3B2O3·H2O, nanoribbon, bundle-like nanostructure and fan-shaped non-nanostructure, have been prepared under hydrothermal conditions, which were characterized by XRD, FT-IR, TGA and SEM. Their flame retardant properties to the polypropylene were investigated by thermal analysis method (including TG, DSC and non-isothermal decomposition kinetics) and oxygen index method. With the decrease in TG mass loss, the increase in heat absorption for DSC in N2 atmosphere, the increase in LOI values, and the increase in apparent activation energy Ea, the flame retardant properties of prepared 2CaO·3B2O3·H2O samples increased gradually from non-nanostructure to bundle-like nanostructure and then to nanoribbon. This trend may be ascribed to their sizes being decreased accordingly. The flame retarding mechanism has been proposed. The mechanical property of polypropylene/2CaO·3B2O3·H2O composite material has also been evaluated. It can be predicted that 2CaO·3B2O3·H2O nanoribbon could serve as an excellent flame retardant.