Ventromedial prefrontal cortex (vmPFC) is an important brain region involved in many psychological functions. Previous neuroimaging studies have shown disrupted function and altered metabolic level within vmPFC of schizophrenia (SCZ) patients. However, the linkage between the functional connectivity and its underlying neurobiological mechanism in SCZ remains unclear. In this study, we aimed to investigate the altered relationship between the functional connectivity strength (FCS) and metabolic concentrations within vmPFC in drug-naïve first-episode psychosis (FEP) patients using a combined functional magnetic resonance imaging (fMRI) and single-voxel proton magnetic resonance spectroscopy (1H- MRS) technique. There were 26 drug-naïve FEP patients and 27 matched healthy controls participated this study. We have found altered correlation between FCS and N-acetylaspartate (NAA) in drug-naïve FEP patients. In addition, the glutamate and glutamine compounds (Glx) and NAA concentrations were positively correlated with Positive and Negative Symptoms Scale (PANSS) total scores. Our findings revealed the disrupted functional-metabolic coupling within vmPFC in drug-naïve FEP patients and provided useful insights in understanding the etiology of SCZ.