The exquisite soft tissue contrast provided by magnetic resonance imaging arises principally from differences in the intrinsic relaxation properties, T1 and T2. Although the intricate relationships that link tissue microstructure and the longitudinal and transverse relaxation times remain to be firmly established, quantitative measurement of these parameters, also referred to as quantitative relaxometry, can be informative of disease-related tissue change, developmental plasticity, and other biological processes. Further, relaxometry studies potentially offer a more detailed characterization of tissue, compared with conventional qualitative or weighted imaging approaches.The purposes of this review were to briefly review the biophysical basis of relaxation, focusing specifically on the T1, T2, and T2* relaxation times, and to detail some of the more widely used and clinically feasible techniques for their in vivo measurement. We will focus on neuroimaging applications, although the methods described are equally well suited to cardiac, abdominal, and musculoskeletal imaging. Potential sources of error, and methods for their correction, are also touched on. Finally, the combination of relaxation time data with other complementary quantitative imaging data, including diffusion tensor imaging, is discussed, with the aim of more thoroughly characterizing brain tissue.