Melasma is a fairly common condition that is the result of hyperpigmentation caused by increased melanin secretion. In the course of melasma, certain areas of the skin become darker than the rest of the epidermis. Although the pathogenesis remains incompletely clarified, several contributing factors have been identified, namely exposure to ultraviolet and visible light, family predisposition, pregnancy, and the use of exogenous hormones. Since current beauty standards associate healthy skin with its flawless and uniform color, people strive to eliminate any unaesthetic discoloration. Cosmetic and pharmaceutical products containing active substances with a whitening effect then become helpful. The most commonly used for this purpose are hydroquinone, arbutin, retinoids, organic acids (e.g., kojic, azelaic, and ellagic), and vitamins (B3, C, and E). However, the undesirable side effects they cause and the drive to replace synthetic chemicals with their natural counterparts have resulted in numerous reports on extracts of natural origin that exhibit skin-whitening effects. The purpose of this paper is to review the most recent scientific literature, which presents active substances of natural and synthetic origin with potential for the treatment of melasma. In addition, analytical techniques that can be used for qualitative and quantitative analysis of these substances present in cosmetic and pharmaceutical products will also be presented.