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We previously reported that a combined <i>myo</i>-inositol, probiotics, and enriched micronutrient supplement (intervention) taken preconception and in pregnancy reduced postpartum blood loss (PBL) and major postpartum hemorrhage compared with a standard micronutrient supplement (control), as secondary outcomes of the NiPPeR trial. This study aimed to identify the intervention components that may contribute to this effect. Associations of plasma concentrations of <i>myo</i>-inositol and vitamins B2, B6, B12, and D at preconception (before and after supplementation), early (~7-weeks), and late pregnancy (~28-weeks) with PBL were assessed by multiple linear regression, adjusting for site, ethnicity, preconception BMI, parity, and previous cesarean section. Amongst 583 women, a higher concentration of <i>myo</i>-inositol in early pregnancy was associated with a PBL reduction [β_adj −1.26 (95%CI −2.23, −0.29) mL per µmol/L <i>myo</i>-inositol increase, <i>p</i> = 0.011]. Applying this co-efficient to the increase in mean 7-week-<i>myo</i>-inositol concentration of 23.4 µmol/L with the intervention equated to a PBL reduction of 29.5 mL (~8.4% of mean PBL of 350 mL among controls), accounting for 84.3% of the previously reported intervention effect of 35 mL. None of the examined vitamins were associated with PBL. Therefore, <i>myo</i>-inositol may be a key intervention component mediating the PBL reduction. Further work is required to determine the mechanisms involved.