Background: Advances in computed tomography (CT) technology, particularly photon-counting CT (PCCT), are reshaping the possibilities for medical imaging. PCCT in spectral imaging enables the high-resolution visualization of tissues with material-specific accuracy. This study aims to establish a foundational approach for the in vivo visualization of intracranial blood using PCCT, focusing on non-enhanced imaging techniques and spectral imaging capabilities. Methods: We employed photon-counting detector within a spectral CT framework to differentiate between venous and arterial intracranial blood. Our analysis included not only monoenergetic +67 keV reconstructions, but also images from virtual non-contrast and iodine phases, enabling detailed assessments of blood’s characteristics without the use of contrast agents. Results: Our findings demonstrate the ability of PCCT to provide clear and distinct visualizations of intracranial vascular structures. We quantified the signal-to-noise ratio across different imaging phases and found consistent enhancements in image clarity, particularly in the detection and differentiation of arterial and venous blood. Conclusion: PCCT offers a robust platform for the non-invasive and detailed visualization of intravascular intracranial blood. With its superior resolution and specific imaging capabilities, PCCT lays the groundwork for advancing clinical applications and research, notably in the diagnosis and management of intracranial disorders. This technology promises to improve diagnostic accuracy by enabling more precise imaging assessments.