We studied the hemodynamic and metabolic changes, underlying paradoxical effect of Zolpidem, in a patient in Persistent Vegetative State (PVS), using magnetic resonance imaging (MRI) based on BOLD signal and proton spectroscopy (1H-MRS). Significantly increased BOLD signal were transiently localized in frontal cortex. Increased levels of N-Acetyl-Aspartate, Glutamine-Glutamate and Lactate were localized in the same region. Significant linear correlations between BOLD signal and metabolites concentrations were found. We discussed that Zolpidem attaches receptors of the neurodormant cells, leading a dormancy switched off and inducing brain activation. We concluded that 1H-MRS and BOLD signal assessment might contribute to study neurovascular coupling in PVS cases after Zolpidem administration.