Orthorhombic Nb2O5 (T-Nb2O5) nanocrystallites are successfully fabricated through evaporation induced self-assembly (EISA) method guided by a commericalised triblock copolymer – Pluronic F127. We demonstrate a morphology transition of T-Nb2O5 from continuous porous nanofilm to monodisperse nanoparticle by changing the content of Pluronic F127. The electrochemical results show that the optimized monodisperse of Nb-2 with particle size of 20 nm achieve premier Li-ion intercalation kinetics and higher rate capability than mesoporous T-Nb2O5 nanofilms. Nb-2 present an initial intercalation capacity of 528 and 451 C g-1 at current densities of 0.5 and 5 A g-1 and performed stable capacity of 499 C g-1 after 300 charge/discharge cycles and 380 C g-1 after 1000 cycles, respectively. We would expect this copolymer guided monodispersing of T-Nb2O5 nanoparticles with high Li+ intercalation performance to open up new window for novel EES technologies.