Various MRI techniques, including myelin water imaging, T1w/T2w ratio mapping and diffusion-based imaging can be used to characterize tissue microstructure. However, surprisingly few studies have examined the degree to which these MRI measures are related within and between various brain regions. Therefore, whole-brain MRI scans were acquired from 31 neurologically-healthy participants to empirically measure and compare myelin water fraction (MWF), T1w/T2w ratio, fractional anisotropy (FA), axial diffusivity (AD), radial diffusivity (RD) and mean diffusivity (MD) in 25 bilateral (10 grey matter; 15 white matter) regions-of-interest (ROIs). Except for RD vs. T1w/T2w, MD vs. T1w/T2w, moderately significant to highly significant correlations (p < 0.001) were found between each of the other measures across all 25 brain structures [T1w/T2w vs. MWF (Pearson r = 0.33, Spearman ρ = 0.31), FA vs. MWF (r = 0.73, ρ = 0.75), FA vs. T1w/T2w (r = 0.25, ρ = 0.22), MD vs. AD (r = 0.57, ρ = 0.58), MD vs. RD (r = 0.64, ρ = 0.61), AD vs. MWF (r = 0.43, ρ = 0.36), RD vs. MWF (r = −0.49, ρ = −0.62), MD vs. MWF (r = −0.22, ρ = −0.29), RD vs. FA (r = −0.62, ρ = −0.75) and MD vs. FA (r = −0.22, ρ = −0.18)]. However, while all six MRI measures were correlated with each other across all structures, there were large intra-ROI and inter-ROI differences (i.e., with no one measure consistently producing the highest or lowest values). This suggests that each quantitative MRI measure provides unique, and potentially complimentary, information about underlying brain tissues – with each metric offering unique sensitivity/specificity tradeoffs to different microstructural properties (e.g., myelin content, tissue density, etc.).