The objective of this paper is to investigate the correlation between serum macro-element and trace element contents and bone mineral density (BMD) as well as the occurrence of osteoporosis. After the epidemiological investigation of 290 postmenopausal women from ages 45 to 65 in the Xi'an urban area, their blood was collected and serum concentrations of macro-elements, calcium, phosphonium, potassium, sodium, magnesium, and trace elements, zinc, iron, copper, and selenium were determined using atomic absorption spectrometry. Their BMD was measured by QDR-2000 dual-energy X-ray absorptiometry (DEXA). The correlation analysis between BMD and serum element contents was done with the software of SPSS 13.0. The correlation analysis of serum elements of postmenopausal women showed that there was a significant correlation between serum calcium and the other elements, and also a significant correlation between serum phosphonium and the others except serum potassium. The serum potassium content had a significant correlation with serum calcium, sodium and iron, but sodium content showed a significant correlation with the others except iron and selenium. In addition, copper had a significant correlation with the others except potassium and selenium. In correlation analysis between BMD and the elements contents, only did the potassium content show a significant positive correlation with BMD of lumbar vertebra and proximal femora. The comparison results between osteoporosis group, osteopenia group, and healthy group showed that there was no significant difference in the element contents between the groups, but there existed a tendency that potassium content increased with the rise of BMD. There exist significant correlations between the contents of serum elements such as calcium, phosphonium, sodium, potassium, magnesium, zinc, iron, copper, and selenium, but no significant differences in these elements contents between the osteoporosis group, osteopenia group, and healthy group. Serum potassium content shows a significant positive correlation with BMD, suggesting potassium may be involved in the development of osteoporosis in postmenopausal women.