Xylans are major components of land plant secondary cell walls and are required for normal plant growth and development. Secondary walls also account for the bulk of lignocellulosic biomass, a potential feedstock for large-scale production of biofuels. Glucuronoxylan and arabinoxylan affect the conversion of lignocellulosic biomass to fermentable sugar, a crucial and expensive step in biofuel production. Thus, knowledge of xylan biosynthesis may provide tools to modify secondary cell wall structure and thereby improve the bioprocessing characteristics of biomass. Recent studies have shown that glucuronoxylan structure and biosynthesis are far more complex than previously appreciated and the number of glycosyltransferases implicated in this process continues to increase. New hypotheses regarding the mechanisms of glucuronoxylan biosynthesis challenge some widely held views.