Objectives: This study developed and validated reference materials (RMs) to analyze metal compounds in blood. Methods: We referred to KoNEHS (Korea National Environmental Health Survey) to estimate concentrations of blood metals (cadmium, Cd; lead, Pb; mercury, Hg) and applied analytical methods (inductively coupled plasma - mass spectroscopy, ICP-MS, for Cd and Pb; graphite furnace - atomic absorption spectrometry, GF-AAS, for Cd and Pb; and direct mercury analyzer, DMA, for Hg). Homogeneity and stability tests were carried out. In addition, certified values and uncertainties of RMs were calculated through internal and external experiments. All RMs were developed and assessed in various forms according to element, analytical method, and two types of concentration levels high concentration for occupational exposure and low concentration for environmental exposure. Results: All samples showed acceptable homogeneity, except for low concentration of Cd in the GF-AAS method. Short- and long-term stabilities were satisfied by ANOVA testing. In the inter-laboratory comparison, robust medians were lower than the certified values of all RMs (robust median/reference value; $1.301/1.327{\mu}g/L$ for Cd, ICP-MS, low concentration; $3.152/3.388{\mu}g/L$ for Cd, ICP-MS, high concentration; $1.219/1.301{\mu}g/L$ for Cd, GF-AAS, low concentration; $3.074/3.321{\mu}g/L$ for Cd, GF-AAS, high concentration; $14.473/14.516{\mu}g/L$ for Pb, ICP-MS, low concentration; $50.069/50.114{\mu}g/L$ for Pb, ICP-MS, high concentration; $12.881/14.147{\mu}g/L$ for Pb, GF-AAS, low concentration; $47.015/47.591{\mu}g/L$ for Pb, GF-AAS, high concentration; $4.059/4.218{\mu}g/L$ for Hg, DMA, low concentration; $11.474/11.181{\mu}g/L$ for Hg, DMA, high concentration). Conclusion: This study demonstrates procedures for developing and validating RMs for biomonitoring in the field of the environmental health.