Essential trace metals (ETMs) may play important roles in the pathophysiology of benign and malignant breast cancers. Our study aimed to find associations between ETMs and benign and malignant breast cancers. We recruited 146 patients with benign (n = 73) and malignant (n = 73) breast tumors and 95 healthy controls (HCs) from Peking University Third Hospital, Beijing, China. The serum concentrations of seven ETMs (Zn, Mn, Cu, Fe, Co, Ni, and Mo) were evaluated using inductively coupled plasma mass spectrometry (ICP-MS). The serum concentrations of Zn were significantly lower in the malignant group than in the HC group, whereas the concentrations of Cu (p < 0.001) were significantly higher in the malignant group. The concentrations of Fe were significantly lower in both malignant and benign groups than in the HC group (p < 0.05). We observed that the Fe/Cu ratio was lower and the Cu/Ni ratio was higher in the malignant group than in the HCs, as well as in the benign group than in the HCs. The serum concentration of Fe (OR = 0.454; 95% CI, 0.263, 0.784; p = 0.005) was negatively associated with breast tumors after adjusting for potential confounders, including age, BMI, and smoking, drinking and menopause statuses; that of Cu (OR = 2.274; 95% CI, 1.282, 4.031; p = 0.005) was positively associated. Changes in the concentrations of ETMs (Zn, Cu, Fe, and Ni) may be involved in the development of malignant breast cancer. The findings provide foundations for further exploration of ETMs in the prevention and treatment of breast tumors.