Postpartum depression (PPD) is a serious mental health issue among women after childbirth, and screening systems that incorporate questionnaires have been utilized to screen for PPD. These questionnaires are sensitive but less specific, and the additional use of objective measures could be helpful. The present study aimed to verify the usefulness of a measure of autonomic function, heart rate variability (HRV), which has been reported to be dysregulated in people with depression. Among 935 women who had experienced childbirth and completed the Edinburgh Postnatal Depression Scale (EPDS), HRV was measured in EPDS-positive women (n = 45) 1 to 4 weeks after childbirth using a wearable device. The measurement was based on a three-behavioral-state paradigm with a 5 min duration, consisting of rest (Rest), task load (Task), and rest-after-task (After) states, and the low-frequency power (LF), the high-frequency power (HF), and their ratio (LF/HF) were calculated. Among the women included in this study, 12 were diagnosed with PPD and 33 were diagnosed with adjustment disorder (AJD). Women with PPD showed a lack of adequate HRV regulation in response to the task load, accompanying a high LF/HF score in the Rest state. On the other hand, women with AJD exhibited high HF and reduced LF/HF during the After state. A linear discriminant analysis using HRV indices and heart rate (HR) revealed that both the differentiation of PPD and AJD patients from the controls and that of PPD patients from AJD patients were possible. The sensitivity and specificity for PPD vs. AJD were 75.0% and 90.9%, respectively. Using this paradigm, an HRV measurement revealed the characteristic autonomic profiles of PPD and AJD, suggesting that it may serve as a point-of-care sensing tool in PPD screening systems.