Despite the high incidence of major depressive disorder (MDD) in females, the detailed neurobiology mechanism remains not fully understood. Increasing evidence showed that MDD was associated with hippocampal volumetric abnormality with different subfields demonstrating various alteration features. However, the linkage between hippocampal atrophy with its biochemical information remains unclear. In this study, we aim to investigate the relationship between bilateral hippocampal subfields volumetric and metabolic information in female MDD patients, using a combined T1-weighted magnetic resonance imaging (MRI) and proton magnetic resonance spectroscopy (H-MRS) technology. There are 15 female MDD patients and 12 matched healthy controls involved in the study. We found a significant decrease in left fimbria volume in MDD group, which was negatively correlated with left hippocampal choline level. In addition, the left hippocampal creatine concentration in patients was negatively correlated with left fimbria volume. Moreover, the NAA level in left hippocampus was negatively correlated with MDD clinical symptomology including anxiety and depression scores. Our findings suggest that the altered coupling between hippocampal structural and metabolic features might contribute to the etiology of female MDD patients.