The phase relation studies in the Y 2O 3–Nd 2O 3 system has been established after slow cooling of the samples from 1400 °C. Three phase regions, namely a C-type cubic solid solution, a monoclinic solid solution and a biphasic mixture of these two phase fields were observed in this system. An important observation of this investigation is the stabilization of B-type monoclinic phase of Nd 2O 3 on substitution of about 10 mol% Y 3+. A nominal Nd 0.90Y 0.10O 1.5 composition from the monoclinic type solid solution phase region was characterized by the Rietveld refinement of the observed powder XRD data. The typical refined unit cell parameters for this nominal composition are: 14.2761(3), 3.6449(1), 8.9022(2) Å and β = 100.391(2)°, V = 455.62(2) Å 3. The refined results confirm the monoclinic rare-earth oxide structure with Nd 3+ with seven coordinated (capped distorted trigonal prism type) polyhedra and six coordinated (trigonal prism) polyhedra. The crystal structure is built from the edge sharing of these polyhedra. The striking observation of the refinement is that the Y 3+ prefers six coordinated polyhedral site instead of randomly distributed over all the Nd 3+ sites, which is accounted by the smaller ionic radii of Y 3+ compared to the Nd 3+ ions. The further details of the trend in phase relation in Nd 2O 3–Y 2O 3 system has been explained on the basis of the crystal structure and ionic radii of the metal ions.