In 2021, the first clinical photon-counting CT (PCCT) was introduced. The purpose of this study is to evaluate the image quality of polyenergetic and virtual monoenergetic reconstructions in unenhanced PCCTs of the head. A total of 49 consecutive patients with unenhanced PCCTs of the head were retrospectively included. The signals ± standard deviations of the gray and white matter were measured at three different locations in axial slices, and a measure of the artifacts below the cranial calvaria and in the posterior fossa between the petrous bones was also obtained. The signal-to-noise ratios (SNRs) and contrast-to-noise ratios (CNRs) were calculated for all reconstructions. In terms of the SNRs and CNRs, the polyenergetic reconstruction is superior to all virtual monoenergetic reconstructions (p < 0.001). In the MERs, the highest SNR is found in the 70 keV MER, and the highest CNR is in the 65 keV MER. In terms of artifacts below the cranial calvaria and in the posterior fossa, certain MERs are superior to polyenergetic reconstruction (p < 0.001). The PCCT provided excellent image contrast and low-noise profiles for the differentiation of the grey and white matter. Only the artifacts below the calvarium and in the posterior fossa still underperform, which is attributable to the lack of an artifact reduction algorithm in image postprocessing. It is conceivable that the usual improvements in image postprocessing, especially with regard to glaring artifacts, will lead to further improvements in image quality.