Dielectric and structural properties have been studied for solution-mixed PVDF/PMMA polyblend samples up to a maximum PVDF weight fraction (W) 0.4. Crystallization of PVDF has been observed in polyblends with PVDF weight fractions 0.4 and 0.3. Analysis of XRD results shows that the pure PVDF as well as the polyblend samples (with W = 0.3 and 0.4) have phase III PVDF crystals. Dielectric parameters, ε′ and ε″, have been measured in the temperature range 40°–140°C and frequency range 100 Hz-1 MHz. The dielectric constant of the polyblend samples falls in between those of the pure components and increases with the PVDF content. The dielectric loss thermograms of PMMA show the β relaxation of the polymer, which may have contribution from the α relaxation also. A part of the αarelaxation of PVDF is observed in its dielectric loss thermograms. A small hump is observed in the dielectric loss thermograms of the polyblends which could be due to the β relaxation of PMMA and the glass transition of the amorphous phase of the polyblends. Charge carrier trapping appears to make a large contribution to the dielectric parameters.