Diffusion tensor imaging (DTI) showed its adequacy in evaluating the normal-appearing white matter (NAWM) and lesions in the brain that are difficult to evaluate with routine clinical magnetic resonance imaging (MRI) in multiple sclerosis (MS). Recently, MRI systems have been developed with regard to software and hardware, leading to different proposed diffusion analysis methods such as diffusion tensor imaging, q-space imaging, diffusional kurtosis imaging, neurite orientation dispersion and density imaging, and axonal diameter measurement. These methods have the ability to better detect in vivo microstructural changes in the brain than DTI. These different analysis modalities could provide supplementary inputs for MS disease characterization and help in monitoring the disease’s progression as well as treatment efficacy. This paper reviews some of the recent diffusion MRI methods used for the assessment of MS in vivo.