Non-inflammatory vascular diseases of the central nervous system (CNS), including small vessel diseases, hereditary vasculopathies, and ischemic strokes, may closely mimic multiple sclerosis (MS) and other neuroinflammatory disorders in both clinical and radiological presentations. This chapter offers a comprehensive overview of cerebral amyloid angiopathy (CAA), cerebral autosomal dominant arteriopathy with subcortical infarcts and leukoencephalopathy (CADASIL), cerebral small vessel disease (CSVD), monogenic vasculopathies such as COL4A1-related disorders, ischemic stroke, migraine, Moyamoya disease and syndrome, posterior reversible encephalopathy syndrome (PRES), superficial siderosis of CNS, and vascular myelopathy. Detailed discussions are provided on epidemiology, pathophysiology, clinical manifestations, imaging features, cerebrospinal fluid findings, and diagnostic criteria. Characteristic imaging findings such as lobar microbleeds in CAA, anterior temporal lobe lesions in CADASIL, and lacunar infarcts and white matter hyperintensities in CSVD are emphasized. The chapter also highlights red flags that help differentiate vascular diseases from inflammatory demyelination, such as lesion symmetry, lack of enhancement, and absence of spinal cord or optic nerve involvement. The diagnostic utility of central vein sign (CVS), optical coherence tomography (OCT), and genetic testing is also discussed. Recognition of these vascular mimics is critical to avoid misdiagnosis and inappropriate immunosuppression, which can worsen outcomes. This chapter provides neurologists with essential tools for differential diagnosis, supporting accurate identification and management of vascular CNS diseases mimicking inflammatory demyelination.