Levulinic acid derived compounds are important energy chemicals and intermediates which possess industrial potential applications. Levulinate compounds are mainly used in fuel-formulations because of their properties such as non-toxicity, high-lubricity, better density, low-vapor pressure, low-viscosity and boiling-point/flash-point/cloud-point stability under cold conditions. Moreover, oxygenated levulinate blending reduces pollutants like NOx and particulate matter emissions. The literature shows synthesis of these levulinates using highly acidic and various metal derivatives at higher temperatures. In the present study, we have investigated an enzymatic synthesis of various levulinates in non-aqueous media providing up to 94-99% yield at 45 degrees C which offers several advantages over conventional chemical synthesis such as mild reaction conditions, low-energy requirements, minimal waste-disposal, easy down-streaming and biocatalyst reusability. All reaction parameters are optimized in detail such as: alcohol (4 mmol); levulinic acid (7 mmol); solvent: MTBE 2.5 mL; biocatalyst: 120 mg; temperature 45 degrees C and time 8 h to achieve the highest yield. Moreover, we have performed thermo-chemical energy investigation (EA, Delta H-#, Delta S-#, Delta G(#)) of the present methodology in various solvents and for synthesis of various levulinate compounds. The biocatalyst was efficiently recycled up to 5 cycles. Furthermore, protocol was applied for the synthesis of various valuable fuel additive levulinates. (C) 2015 Elsevier B.V. All rights reserved.