Angle-dispersive X-ray diffraction and Fourier transform infrared spectroscopy have been employed to study the phase diagram of urea crystal beyond 15 GPa and at temperatures in excess of 400 K. Previously reported Bridgman phase II was structurally characterized for the first time, and it is discovered that it coincides with room-temperature phase IV. Large metastability P–T regions were identified for all phases in the sequence I–III–IV–V, ascribed to the difficulty to disrupt the H-bonding network, a prerequisite to accomplish the molecular rearrangement necessary for the structural transformation. High-temperature studies and use of a hydrostatic compression medium allows the thermodynamic boundaries of phase III, and partly of phase IV, to be identified therefore making a considerable step forward in the knowledge of the phase diagram of urea.