Alternative and green energy resources are needed to replace the rapidly depleting and non-renewable fossil fuels. The abundant and renewable lignocellulosic biomass can be converted into value-added chemicals and biofuels, which are currently made from non-renewable fossil fuels. The conversion of lignocellulosic biomass on heterogeneous catalysts was investigated in detail using various catalytic processes. In particular, the solid acid catalysts, which have both Lewis and Brønsted acid sites, have attracted significant research interests. Among these catalysts, metal phosphates are of particular interest because of their relatively simple synthetic routes, low cost, environmental friendliness, and tunable Lewis and Brønsted acid sites. In this tutorial, we have given a brief overview of the synthetic methods and summarized various catalytic processes involved in biomass processing, including dehydration, oxidation, transfer hydrogenation, transesterification, hydrogenolysis and hydrodeoxygenation on metal phosphate catalysts to produce value-added chemicals and biofuels. The main focus is to highlight the relationship between the structural properties of the catalysts and their catalytic properties and to clarify future research opportunities in this exciting area.