As an alternative to second generation ethanol, valeric esters can be produced from lignocellulose through levulinic acid. While some data on these fuels are available, only few experiments have been performed to analyze their combustion characteristics under engine conditions. Using a traditional spark ignition engine converted to mono-cylinder operation, we have investigated the engine performances and emissions of methyl and ethyl valerates. This paper compares the experimental results for pure valeric esters and for blends of 20% of esters in PRF95, with PRF95 as the reference fuel. The esters propagate faster than PRF95 which requires a slight change of ignition timing to optimise the work output. However, both the performances and the emissions are not significantly changed compared to the reference. Accordingly, methyl and ethyl valerate represent very good alternatives as biofuels for SI engines. Future studies will focus on testing these esters in real application engines and performing endurance tests.