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To investigate longitudinal relaxation times and saturation-transfer effects of phosphorous metabolites in breast fibroglandular tissue in vivo with 31P MR spectroscopy at 7T.Progressive saturation with adiabatic half passage excitation was used to determine T1 values of 31P metabolites in a group of six healthy volunteers. Saturation-transfer experiments were performed in seven healthy volunteers by saturating at 0 ppm and 10 ppm with sinc-Gaussian pulses (90 ms; 10-ms pulse interval; B1 = 17 μT) prior to excitation. Localization was performed by surface coils and one-dimensional chemical shift imaging. Data were analyzed via spectral fitting with the JMRUI software package, and T1 values were obtained by fitting the data to the signal equation.The determined longitudinal relaxation time values at 7T were as follows: phosphoethanolamine, 4.0 ± 0.2 s; phosphocholine, 1.8 ± 0.2 s; inorganic phosphate, 6.1 ± 0.1 s; phosphodiesters, glycerophosphatidylethanolamine plus glycerophosphocholine, 2.1 ± 0.1, and glycerophosphatidylethanolamine, 1.5 ± 0.1s; γ-ATP, 2.1 ± 0.1 s; and α-ATP, 2.0 ± 0.1 s. Saturation-transfer measurements with saturation pulses at 0 ppm showed a significant signal reduction in the phosphodiester 2–3 ppm range, whereas the γ-ATP signal at −2.5 ppm was not affected significantly.Longitudinal relaxation times of phosphorous metabolites in fibroglandular tissue revealed relatively low T1 values for phosphodiesters. Saturation-transfer measurements showed that the phosphodiester signals were the only signals that were affected significantly, possibly indicating the presence of mobile phospholipids. Magn Reson Med 76:402–407, 2016. © 2015 Wiley Periodicals, Inc.