Increasing the range of fuels and bioproducts that are derived from lignocellulosic biomass and the efficiency at which they are produced hinges on a detailed understanding of the cell wall biosynthetic process. Herein, we review the structure and biosynthesis of lignocellulosic biomass and also highlight recent breakthroughs that demonstrate a complex regulatory system of transcription factors, small interfering RNAs and phosphorylation that ultimately dictate the development of the polyalaminate cell wall. Finally, we provide an update on cases where plant biotechnology has been used to improve lignocellulosic biomass utilization as a second-generation biofuel source.