In this study, we report the effect of intercalation of dimethyl sulfoxide (DMSO) and urea molecules into the interlayer space of Ti3C2Tx MXene on the dielectric properties of poly(vinylidene fluoride) (PVDF)/MXene polymer nanocomposites. MXenes were obtained by a simple hydrothermal method using Ti3AlC2 and a mixture of HCl and KF, and they were then intercalated with DMSO and urea molecules to improve the exfoliation of the layers. Then, nanocomposites based on a PVDF matrix loading of 5–30 wt.% MXene were fabricated by hot pressing. The powders and nanocomposites obtained were characterized by using XRD, FTIR, and SEM. The dielectric properties of the nanocomposites were studied by impedance spectroscopy in the frequency range of 102–106 Hz. As a result, the intercalation of MXene with urea molecules made it possible to increase the permittivity from 22 to 27 and to slightly decrease the dielectric loss tangent at a filler loading of 25 wt.% and a frequency of 1 kHz. The intercalation of MXene with DMSO molecules made it possible to achieve an increase in the permittivity up to 30 at a MXene loading of 25 wt.%, but the dielectric loss tangent was increased to 0.11. A discussion of the possible mechanisms of MXene intercalation influence on the dielectric properties of PVDF/Ti3C2Tx MXene nanocomposites is presented.