Mismatch negativity (MMN) component of the event-related brain potentials has become popular in cognitive and clinical brain research during the recent years. It is an early response to a violation of an auditory rule such as an infrequent change in the physical feature of a repetitive sound. There is a lot of evidence on the association of the MMN parameters and behavioral discrimination ability, although this relationship is not always straight-forward. Since the MMN reflects sound discrimination accuracy, it can be used for probing how well different groups of individuals perceive sound differences, and how training or remediation affects this ability. In the present review, we first introduce some of the essential MMN findings in probing sound discrimination, memory, and their deficits. Thereafter, issues which need to be taken into account in MMN investigations as well as new improved recording paradigms are discussed.