Studies of nectar sugar composition in the Proteaceae, an ancient southern hemisphere plant family, have demonstrated that xylose comprises up to 39% of nectar sugar in two genera, Protea and Faurea, and may therefore represent a substantial fraction of the energy available to pollinators of these plants. Although insect and bird pollinators of Protea species are averse to xylose, mice (Aethomys namaquensis) will drink pure xylose, which is metabolized either by gut bacteria or by the mouse tissues. In the form of xylan polymers, the pentose sugar D-xylose is a structural component of plant cell walls, and there is considerable biotechnological interest in xylose fermentation. Bacteria and yeasts convert D-xylose to D-xylulose and thence via the pentose phosphate pathway to fructose-6-phosphate, which is either oxidized or fermented to ethanol. Gut symbionts of rodent pollinators may be analogous to ruminal xylose-metabolizing bacteria. The presence of xylose in Protea and Faurea nectar remains puzzling in view of pollinator aversions: even for rodent pollinators, it is the least preferred nectar sugar. In the generalized pollination systems of the Proteaceae, a coevolutionary explanation for nectar xylose as an attractant for mammalian pollinators is probably less likely than one involving plant physiology, with xylose in phloem sap being secreted passively into the nectar.