We describe a new method for assessing the Ca/P ratio of bone in vivo using gamma-ray photon absorptiometry. The theoretical approach of the method and the estimation of the variance are presented. Two radiation sources, Gd-153 (100 keV), and I-125 (27.5 keV), and a germanium detector were used to determine this ratio. Measurements were made on bone phantoms with different Ca/P ratios; also, the ratio was measured on lamb and sheep tibias, rabbit tibias, and human fingers. Since the accuracy of the method is affected by the amount of fat and collagen in the measurement field, the effect of collagen and fat on the measurements also was investigated. In all cases, the precision of the method, expressed as the coefficient of variation (CV): 100x standard deviation/mean, was near to the theoretical one, ranging from 1.8% to 3.2%. For human fingers, the CV was 3.2%, a value near to the theoretical 2.9% with a dose to the skin ranging from 0.044 to 0.066 mGy, depending on the width of the finger.