Three-material decomposition is crucial for material quantification when more than two elemental materials, including a K-edge material, are presented in an image object. In principle, threematerial decomposition requires a triple energy scan which cannot be directly accomplished using a conventional dual energy CT system. In this work, a new scheme to enable three-material decomposition by employing phase contrast CT was presented. When a grating interferometer is added, a conventional absorption dual energy CT system can be upgraded to a phase contrast dual energy CT system which provides an additional phase signal related to the real part of the refractive index of an image object, along with the absorption signal under two different x-ray spectra. In this work, a three-material decomposition method was proposed for the aforementioned dual energy phase contrast CT system. Physical experimental studies were performed on a benchtop x-ray Talbot-Lau interferometer system to validate the proposed method. A physical phantom, containing calcium and iodine inserts of known concentrations, was used as the image object. A rotation-rotation dual energy phase contrast CT scan was performed under 40 and 80 kVp tube potentials. For each view angle, a phase stepping procedure with five phase steps was performed. After the phase retrieval procedure and image reconstruction using the standard filtered-back projection, the solutions were decomposed into the calcium, iodine and water bases based on the proposed decomposition method. For all the solutions, the relative quantification errors of the concentrations were within 10%.