The flowers of Polemonium caeruleum are protandrous. The nectary is in the form of a rim encircling the ovary. Secreted nectar accumulates in a chamber located at the bottom of the floral tube and is protected by dense staminal hairs. The nectary tissue is not vascularized, but is supplied by vascular strands that occur near the base of the nectary and which directly supply the stamens. Nectar is secreted via modified stomata located on the upper part of the rim, particularly on the adaxial surface. The number of stomata and the volume and sugar concentration of nectar are greater during the female stage than during the male stage. In both stages, however, the nectar is sucrose-dominant. This paper shows that in P. caeruleum the nectar sugars are not a direct product of current photosynthesis, since plastids of nectary cells are devoid of chlorophyll. The main source of sugars in secreted nectar is the phloem sap, together with starch that accumulates in the nectary cells during the male stage and is then rapidly hydrolyzed during the female stage.