Poly ( vinylidene fluoride ) ( PVdF )-based gel polymer electrolytes with various compositions were prepared by solution casting technique. The kinetics of gelation was analyzed via the correlation between the apparent gelation rate and concentration of PVdF at a given temperature.Combination the results of the kinetics of gelation and the DSC study, it revealed that the phase separation was the major behavior and the fibrils were the major junction joints of the three-dimensional network even in the ease the concentration of PVdF was higher than 25 wt%. The porous surface observed by ESEM also reflected that the phase separation took place during the gelation.