Background: Cesarean delivery is commonly performed under either spinal or general anesthesia. While both techniques are widely used, their differential effects on maternal neurochemical profiles, particularly excitatory neurotransmitters such as glutamate, remain incompletely understood. Glutamate plays a central role in stress response, nociception, and neuroendocrine regulation. This study aimed to compare maternal salivary glutamate concentrations between spinal and general anesthesia during cesarean delivery. Method: In this prospective study, 66 women undergoing cesarean delivery were included: 32 received spinal anesthesia and 34 received general anesthesia. Unstimulated saliva samples were collected perioperatively and analyzed using a colorimetric enzymatic assay. Clinical and demographic variables were extracted from electronic medical records. Results: Baseline maternal and neonatal characteristics were comparable between groups (all p > 0.05). Glutamate concentrations were not normally distributed. Median salivary glutamate levels were significantly higher in the general anesthesia group compared with the spinal anesthesia group (8.05 nmol/µL [IQR 4.81–11.69] vs. 5.19 nmol/µL [IQR 3.05–8.39]; p = 0.041) After adjustment for maternal and perinatal covariates, anesthesia type was not independently associated with glutamate levels (p = 0.21). Conclusion: General anesthesia was associated with higher unadjusted maternal salivary glutamate levels compared with spinal anesthesia during cesarean delivery; however, this association did not persist after multivariable adjustment. These findings suggest that anesthesia technique alone may not independently influence perioperative glutamatergic responses. Further research is warranted to clarify the clinical significance of these neurochemical changes for maternal and neonatal outcomes.