Abstract Purpose Nonenhanced computed tomography (CT) of the head is among the most commonly performed CT examinations. The spectral information acquired by photon counting CT (PCCT) allows generation of virtual monoenergetic images (VMI). At the same time, image noise can be reduced using quantum iterative reconstruction (QIR). In this study, the image quality of VMI was evaluated depending on the keV level and the QIR level. Furthermore, the influence of the cranial calvaria was investigated to determine the optimal reconstruction for clinical application. Methods A total of 51 PCCT (NAEOTOM Alpha, Siemens Healthineers, Erlangen, Germany) of the head were retrospectively analyzed. In a quantitative analysis, gray and white matter ROIs were evaluated in different brain areas at all available keV levels and QIR levels with respect to signal, noise, signal-to-noise ratio (SNR), and contrast-to-noise ratio (CNR). The distance to the cranial calvaria of the ROIs was included in the analysis. This was followed by a qualitative reading by five radiologists including experienced neuroradiologists. Results In most ROIs, signal and noise varied significantly between keV levels (p < 0.0001). The CNR had a focal maximum at 66 keV and an absolute maximum at higher keV, slightly differently located depending on ROI and QIR level. With increasing QIR level, a significant reduction in noise was achieved (p < 0.0001) except just beneath the cranial calvaria. The cranial calvaria had a strong effect on the signal (p < 0.0001) but not on gray and white matter noise. In the qualitative reading, the 60 keV VMI was rated best. Conclusion In nonenhanced PCCT of the head the selected keV level of the VMI and the QIR level have a crucial influence on image quality in VMI. The 60 keV and 66 keV VMI with high QIR level provided optimal subjective and objective image quality for clinical use. The cranial calvaria has a significant influence on the visualization of the adjacent brain matter; currently, this substantially limits the use of low keV VMIs (< 60 keV).