As bioethanol from sugarcane and wheat falls out of favour due to concerns about food security, research is ongoing into genetically engineering model plants and microorganisms to find the optimum cell wall structure for the ultimate second generation bioethanol crop. Charis Cook and Alessandra Devoto highlight here the progress made to tailor the plant cell wall to improve the accessibility of cellulose by acting on the regulation, the structure or the relative composition of other cell wall components to ultimately improve saccharification efficiency. They also consider possible side effects of cell wall modification and focus on the latest advances made to improve the efficiency of digestion of lignocellulosic materials by cell wall degrading microorganisms.