The data on density of dilute solutions of urea (U) in ethylene diamine (EDA) with the molality from ∼0.018 to ∼0.39 mol·(kg solvent)−1 were experimentally obtained between (288.15 and 328.15) K and at ambient pressure. The uncertainty in density measurements did not exceed 0.03 kg m–3. The standard (partial at infinite dilution) molar volumes, V2○, and expansibilities, Ep,2○, of U as a solute in EDA were computed. The unusual phenomenon of the thermally activated partial molar isobaric compaction of the solute (PMICS) caused by the presence of a negative sign at Ep,2○ was discovered. The origin of this atypical volumetric effect in both the system under consideration and some other urea-containing amphiprotic media was discussed based on the thermodynamic approach including the Ben-Naim’s concept of the “relative affinity parameter”.