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The herbaceous peony (<i>Paeonia lactiflora</i> Pall.) has high ornamental and nutritional value, and the seeds of <i>P. lactiflora</i> can be used to produce high-quality edible oil. However, low seed yield limits the application of <i>P. lactiflora</i>. This can be mitigated by insect pollinators. Here, we evaluated the pollination services of honeybees (<i>Apis mellifera</i> L.) in a <i>P. lactiflora</i> field. We found that <i>A. mellifera</i> provided pollination for <i>P. lactiflora</i> throughout the day especially in the period from 10:00–15:00. Seed number and weight were significantly increased when <i>P. lactiflora</i> was pollinated by <i>A. mellifera.</i> Furthermore, a DNA barcode, the <i>rbcL</i> gene, was used to analyze pollen samples from the corbiculae (pollen baskets) of <i>A. mellifera</i> (bee pollen, BP) and <i>P. lactiflora</i> flowers (flower pollen, FP). High homology of <i>rbcL</i> genes in the BP and FP suggested that BP was collected from <i>P. lactiflora.</i> Based on our results, <i>A. mellifera</i> provided efficient pollination for <i>P. lactiflora.</i> Therefore, <i>A. mellifera</i> could be a good candidate pollinator for <i>P. lactiflora</i> and could be applied in the field.