In this work, PbS and PbTe nanomaterials with various morphologies were synthesized by a hydrothermal method. The structural properties were investigated by using X-ray diffraction (XRD) and corresponding scanning electron microscopy together with their EDX analysis. Both the PbS and PbTe nanomaterials possess good polycrystalline structure. The crystallite size, determined from the XRD data, of PbS is 5 nm whereas the corresponding value of PbTe is 2.69 nm. SEM micrographs reveal that the prepared PbS nanomaterial has star-shaped structures, micro-flowers, some cubes, and semi-dendrites, whereas PbTe has semi-flower structures. Additionally, the dielectric properties have been studied in a broad frequency range from 0.1 Hz up to 1 MHz at temperatures from 298–423 K. The real and imaginary parts of the complex dielectric constant ε' and ε'' of PbTe are comparatively higher than those of PbS. Moreover, the dielectric data were analyzed on the basis of the electric modulus.