Vitamin B6 is widely used as a first-line treatment for nausea and vomiting of pregnancy (NVP), often combined with doxylamine. This review summarizes its metabolism, proposed mechanisms including neurotransmitter, neuroendocrine, and gut–brain pathways and current evidence on efficacy and safety. While clinical benefits are well supported for mild-to-moderate NVP, the mechanistic role of vitamin B6 remains incompletely understood and requires further biomarker-based research.