Ni‐doped SnO₂ nanoparticles, promising for gas‐sensing applications, have been synthesized by a polymer precursor method. X‐ray diffraction (XRD) and transmission electron microscopy (TEM) data analyses indicate the exclusive formation of nanosized particles with rutile‐type phase (tetragonal SnO₂) for Ni contents below 10 mol%. The mean crystallite size shows a progressive reduction with the Ni content. Room‐temperature Raman spectra of Ni‐doped SnO₂ nanoparticles show the presence of Raman active modes and modes activated by size effects. From the evolution of the A_1g mode with the Ni content, a solubility limit at ∼2 mol% was estimated. Below that content, Raman results are consistent with the occurrence of solid solution (ss) and surface segregation (seg.) of Ni ions. Above ∼2 mol% Ni, the redshift of A_1g mode suggests that the surface segregation of Ni ions takes place. Disorder‐activated bands were determined and their integrated intensity evolution with the Ni content suggest that the solid‐solution regime favors the increase of disorder; meanwhile, that disorder becomes weaker as the Ni content is increased. Copyright © 2010 John Wiley & Sons, Ltd.