The nanostructured Ce1-xZrxO2 solid solutions (x <= 0.2) have been successfully synthesized from CeCl3-ZrCl4-NaOH mixtures by mechanochemical processing as a gradual transformation, involving in-situ CeO2 and amorphous ZrO2 formation as intermediates. Solid solutions type-Ce1-xZrxO2 along with NaCl as diluent were obtained at different milling times, with a final composition of Ce0.8Zr0.2O2 after 5 h and 15 h under high and low energetic milling conditions, respectively. The NaCl formed during the mechanochemical reaction, which is eliminated by washing after calcination of the as-milled sample, allows to obtain a Ce0.8Zr0.2O2 solid solution with high surface area and nanometric grains. The nanostructured Ce0.8Zr0.2O2 solid solution shows good thermal stability after prolonged heating at 600 degrees C. However, the addition of an extra amount of diluent during mechanochemical reaction evidences a detrimental effect, avoiding the formation of solid solution or deteriorating the textural/microstructuctural characteristics of the obtained Ce1-xZrxO2 solid solution. Removal of NaCl previous to calcination improves notably the textural/microstructural characteristics of the Ce0.8Zr0.2O2 solid solution. (C) 2012 Elsevier B.V. All rights reserved.