New-generation biofuels are mainly produced from nonfood crops or waste. Although second-generation ethanol is one of the main options, valeric esters can also be produced from lignocellulose through levulinic acid. However, only few experimental results are available to characterize their combustion behavior. Using a traditional compression ignition (CI) engine converted to monocylinder operation, the engine performances and emissions of butyl and pentyl valerate (BV and PenV, respectively) were investigated. This paper analyses the experimental results for blends of 20%vol of esters in diesel fuel, taking diesel fuel as the reference fuel. The BVand PenV have a smaller cetane number and consequently the ignition delay of the blends is slightly longer. However, engine performances and emissions are not significantly modified by adding 20%vol of esters to diesel fuel. The BV and PenV then represent very good alternative biofuels for CI engines.