Multiple Sclerosis (MS) is a complex disease whose mechanisms of progression still remain unclear. The use of quantitative MRI techniques in a multi-modal fashion, i.e. acquisition of more than one contrast type, can help to non-invasively measure changes in the tissue at a microstructural level during the disease course. Moreover, evidence of spinal cord involvement and its role in the diagnosis and prognosis is mounting. Here, we aim to address both needs by developing a multi-modal qMRI protocol for joint investigation of brain and spinal cord microstructure, and we report findings from a small cohort of people with MS.