Rapid, real-time and on-line detection of Cd in water samples has very important practical significance for preventing water pollution from heavy metals and protecting the safety of human being and ecological environment. X-ray fluorescence spectrometry (XRF) is an important and effective spectroscopy technology for the rapid, real-time and on-line detection of heavy metals. However, for the direct detection of heavy metals in water samples, due to matrix effects, XRF spectrometry has the disadvantages of low signal-to-noise ratio, poor sensitivity and poor stability, which cannot meet the requirements for rapid detection of heavy metals in environmental waters and industrial wastewaters. In order to improve the shortcomings of XRF spectrometry in direct detection of heavy metals in water samples, we selected Chlorella vulgaris as an adsorbent, and innovatively proposed a simple, rapid, economical and environmentally friendly method for the detection of Cd in water based on preconcentration with Chlorella vulgaris combined with energy dispersive X-ray fluorescence (EDXRF) spectrometry. This dataset includes the important data in the study of preconcentration with Chlorella vulgaris combined with energy dispersive X-ray fluorescence spectrometry for rapid determination of Cd in water.Rapid, real-time and on-line detection of Cd in water samples has very important practical significance for preventing water pollution from heavy metals and protecting the safety of human being and ecological environment. X-ray fluorescence spectrometry (XRF) is an important and effective spectroscopy technology for the rapid, real-time and on-line detection of heavy metals. However, for the direct detection of heavy metals in water samples, due to matrix effects, XRF spectrometry has the disadvantages of low signal-to-noise ratio, poor sensitivity and poor stability, which cannot meet the requirements for rapid detection of heavy metals in environmental waters and industrial wastewaters. In order to improve the shortcomings of XRF spectrometry in direct detection of heavy metals in water samples, we selected Chlorella vulgaris as an adsorbent, and innovatively proposed a simple, rapid, economical and environmentally friendly method for the detection of Cd in water based on preconcentration with Chlorella vulgaris combined with energy dispersive X-ray fluorescence (EDXRF) spectrometry. This dataset includes the important data in the study of preconcentration with Chlorella vulgaris combined with energy dispersive X-ray fluorescence spectrometry for rapid determination of Cd in water.