Dielectric spectroscopy can be applied to study the structure and dynamics of block polymer. In this work, dielectric measurements of block copolymer Pluronic L64 solution are carried out in the frequency range between 40 Hz and 110 MHz with variable temperatures and concentrations. We analyze the phase behavior of the PEO13-PPO30-PEO13 (Pluronic L64) aqueous system according to the concentration/temperature-dependence of direct current conductivity. The result indicates the sensitivity of the phase behavior and conductivity of the Pluronic L64 solution to temperature. Besides, two relaxations were observed: relaxation 1 (0.5 MHz) is related to the gelation process, while relaxation 2 (5 MHz) is caused by the interface polarization. On the basis of relaxation 2, the volume fraction and permittivity of the particle were calculated. The formations of the block copolymer micelle and gel are monitored successfully by the temperature/concentration-dependence of the dielectric parameters and the volume fraction.