Betalains are vacuolar pigments composed of a nitrogenous core structure, betalamic acid. Betalamic acid condenses with imino compounds (cyclo-DOPA/its glucosyl derivates) or amino acids/derivates to form violet betacyanins and yellow betaxanthins. These pigments have gained the curiosity of scientific researchers in recent decades. Their importance was increased not only by market orientation toward natural colorants and antioxidants but also by their safety and health promoting properties. To date, about 78 betalains have been identified from plants of about 17 families. In this review, all of the identified pigments are presented, followed by a comprehensive discussion of their structure–activity relationship.