Since Shell company announced its new process in 2010 to produce levulinic acid derivatives from lignocellulose, valerates have been studied in order to assess their capacity as potential fuels for car engines. Since valerates exhibit properties similar to those of engine fuels, they can be used as biofuels or blended with gasoline or diesel. Recent works have focused on determining the properties such as ignition delay, laminar burning speeds, and kinetic schemes to ensure their suitability as fuels. From few studies, it seems that blends of valerates can be used as fuels in SI or compression engines without any drawback, but more real road experiments are needed to improve the real ability of valerates to be used as substitute fuels. As propyl valerate has properties between gasoline and diesel types, studies are also needed to improve it as a potential fuel. It is still not possible to determine whether it is cost effective to produce these products and how better for the world biomass than ethanol production. Moreover, it is still necessary to decide which plant, such as giant reed, would be the most appropriate to produce valerates. This chapter redraws the scientific evolution for these biofuels from the process itself until its potential use.