Cadmium is one of the most harmful elements to human health, and the health of postmenopausal females is an important public health issue. However, the correlation between exposure to cadmium and the survival status of postmenopausal women is currently not fully clear. This research intended to explore the correlation between cadmium exposure and mortality among postmenopausal females using a representative sample of the population in the U.S. We drew upon the data of the National Health and Nutrition Examination Survey (2001–2018). Cox’s proportional hazards models and a restricted cubic spline regression (RCS) model were utilized to analyze the correlation between blood and urine cadmium and the mortality of postmenopausal women. Stratified analyses also were conducted to identify the highest risk factor of mortality for the participants. The mean concentration of blood cadmium was 0.59 μg/L, and the mean concentration of urine cadmium was 0.73 μg/g creatinine. Higher cadmium concentrations in blood and urine were significantly related to an increase in all-cause mortality for postmenopausal females after adjustment for multivariate covariates. Furthermore, there was a linear positive correlation between urine cadmium concentrations and cancer mortality, while there was no correlation between blood cadmium and cancer death. The correlation between cadmium concentrations and all-cause mortality is stronger in older, more overweight women with a history of hypertension or smoking. We propose that cadmium remains an important risk factor of all-cause and cancer mortality among postmenopausal females in the U.S. Further decreases in cadmium exposure in the population can promote the health of postmenopausal women and prolong their lifespan.