Arm symmetrical PbS dendrite （ASD-PbS） nanostructures can be prepared on a large scale by a solvothermal process. The ASD-PbSs exhibit a three-dimensional symmetrical structure, and each dendrite grows multiple branches on the main trunk. Such unique ASD-PbSs can be combined with polyvinylidene fluoride （PVDF） to prepare a composite material with enhanced dielectric and microwave-absorption properties. A detailed investigation of the dependence of the dielectric properties on the frequency and temperature shows that the ASD-PbS/PVDF composite has an ultrahigh dielectric constant and a low percolation threshold. The dielectric permittivity is as high as 1,548 when the concentration of the ASD-PbS filler reaches 13.79 vol.% at 102 Hz, which is 150 times larger than that of pure PVDF, while the composite is as flexible as pure PVDF. Furthermore, the maximum reflection loss can reach -36.69 dB at 16.16 GHz with a filler content of only 2 wt.%, which indicates excellent microwave absorption. The loss mechanism is also elucidated. The present work demonstrates that the addition of metal sulfide microcrystals to polymer matrix composites provides a useful method for improving the dielectric and microwave-absorption properties.