The present study explores the synthesis of butyl levulinate (BL), a green diesel additive, using vanadium‐incorporated Keggin phosphomolybdic acid (HPVM) catalysts. This study highlights the effect of addenda and hydrogen atoms on HPVM catalysts for BL production, thereby elucidating a correlation between addenda atoms, HPVM acidity, and BL yield. The catalysts are characterized using Raman spectroscopy, FTIR, XRD, ammonia‐TPD, SEM‐EDX, and ICP‐OES techniques to determine their structural properties, acidity, and elemental composition. Reaction parameters, including time, temperature, catalyst concentration, stirring rate, and solvent volume, are systematically evaluated to optimize the conversion of levulinic acid (LA) to BL. A significant BL yield (>96%) is obtained using 25 wt.% H4PMo11VO40 (H4PVM) catalyst at 100 °C in 40 min. Kinetic analysis unveiled a pseudo‐first‐order reaction mechanism for BL synthesis with activation energies of 66.73, 68.81, and 71.19 kJ.mol−1 for H4PMo11VO40 (H4PVM), H5PMo10V2O40 (H5PVM), and H6PMo9V3O40 (H6PVM) catalysts, respectively. Additionally, thermodynamic parameters, such as enthalpy of activation (ΔH*), entropy of activation (ΔS*), and Gibbs free energy of activation (ΔG*), are determined. Overall, this study highlights the complex interplay between acidity, activation energy, and BL yield, emphasizing the significance of the number of vanadium addenda atoms in catalyst performance.