The family Apocynaceae is one of the largest and important families in angiosperm. Several members of this family have medicinal properties and have been in the treatment of various ailments. Most of them are consumed as food by tribal people whereas a few plants are used as source of poison. Members of family Apocynaceae are rich in alkaloids, terpenoids, steroids, flavonoids, glycosides, simple phenols, lactones, and hydrocarbons. Other compounds such as sterols, lignans, sugars, lignans, and lactones have been isolated and systematically studied. Few studies have reported antioxidant, anti-inflammatory, antimicrobial, and cytotoxic activities of crude extracts as well as single compound(s) isolated from various members of the family Apocynaceae. Holarrhena antidysenterica, Rauvolfia serpentina, Carissa carandas, and Tabernaemontana divaricata are the extensively studied plants in this family. The present review provides a detailed outlook on ethnopharmacology, phytochemistry, and biological activities of selected members of this family. Moreover, it also covers the biotechnological advances used for large-scale production of bioactive compounds of therapeutic interest along with plant tissue culture-based approaches for conservation of this medicinally valuable family.