Block copolymer blend systems have been of great interest for a wide range of potential applications, such as nanobuilding blocks or guidance materials, because they can provide a rich phase behavior according to external conditions. However, a new and unique phase behavior of block copolymers, which can give us their more extended potential applications, has not yet been reported. Herein, we report the unusual self-assembly of two different types of Pluronic P65 and PE6200 triblock copolymer blends dependent on temperature and PE6200 concentration, which is unique for the block copolymer blends in aqueous solution. As the temperature and concentration of PE6200 (as an additive) increased, the Pluronic P65/PE6200 copolymer blends sequentially self-assembled into an isotropic micellar-hexagonal-isotropic micellar or isotropic micellar-hexagonal-isotropic micellar-lamellar phase, which is a discontinuous ordered phase (called a closed looplike phase transition), and their phase transition temperature could be controlled. To the best of our knowledge, this is the first report of a closed looplike phase transition of Pluronic block copolymer blends in aqueous solution, which can be easily applied to nanosized templates for temperature-selective highly ordered structures and optical devices such as optoelectronics or optical sensors.