The association fibers of the superior longitudinal fasciculus (SLF) connect parietal and frontal cortical regions in the human brain. The SLF comprises of three distinct sub-bundles, each presenting a different anatomical trajectory, and specific functional roles. Nevertheless, in vivo studies of the SLF often consider the entire SLF complex as a single entity. In this work, we suggest a data-driven approach that relies on microstructure measurements for separating SLF-III from the rest of the SLF. We apply the SLF-III separation procedure in three independent datasets using parameters of diffusion MRI (fractional anisotropy), as well as relaxometry-based parameters (T1, T2, T2* and T2-weighted/T1-weighted). We show that the proposed procedure is reproducible across datasets and tractography algorithms. Finally, we suggest that differential crossing with different white-matter tracts is the source of the distinct MRI signatures of SLF-II and SLF-III.