Plants have evolved numerous secretory structures that fulfill diverse roles and shape their interactions with other organisms. Rivea ornata (Roxb.) Choisy (Convolvulaceae) is one species that possesses various external secretory organs hypothesized to be ecologically important. This study, therefore, aimed to investigate five secretory structures (nectary disc, petiolar nectaries, calycinal glands, staminal hairs, and foliar glands) using micromorphology, anatomy, histochemistry, and field observations of plant–animal interactions in order to assess the functional contributions of these structures. Results show that the nectary disc and petiolar nectaries are complex working units consisting of at least epidermis and ground tissue, while the other structures are glandular trichomes. Various groups of metabolites (lipids, phenolic compounds, polysaccharides, terpenoids, flavonoids, and alkaloids) were detected in all structures, while starch grains were only found in the nectary disc, petiolar nectaries, and their adjacent tissues. Integrating preliminary observation of animal visitors with micromorphological, anatomical, and histochemical results, two hypotheses are proposed: (I) nectary disc and staminal hairs are important for pollination as they potentially attract and reward floral visitors, and (II) petiolar nectaries, calycinal glands, and foliar glands contribute to plant defense. Specifically, petiolar nectaries and calycinal glands provide protection from herbivores via guard ants, while calycinal and foliar glands may use plant metabolites to help prevent tissue damage from dehydration and insolation.