The promotional effect of nanosized Ru, Fe, Au, and Mn particles on VOHPO4 x 0.5H2O (VHP) catalytic properties was investigated in benzene hydroxylation reaction using hydrogen hydroperoxide (H2O2) as oxidant. Catalytic results indicated a profound effect of the nanoparticle dopants on VHP catalyst activity and products distribution. Amongst the promoted VHP catalysts, Au/VHP exhibited high catalytic effect with benzene conversion of 76% at a combined 85.5% selectivity toward the formation of phenol and hydroquinone achieved in 6 h under optimised reaction conditions. The extended scope application of nanosized doped Au-VHP showed to provide an effective catalyst for activation of the aromatic hydrocarbons C-H bonds into oxygenate derivatives. The catalyst could be re-used for several cycles with insignificant loss of activity. The doped nanosized Au-VHP catalyst provide a clean promising catalytic route based on heterogeneous catalysis for transformation of aromatics into value-added oxygenates.