The present work represents a significant new approach in the field of thermal spraying to deposit nanostructured phase-pure α-Al2O3 coatings in a single step. In order to understand the mechanism of coating formation, a detailed investigation of in flight formed particles and splat morphologies has been carried out. A plausible deposition mechanism has been proposed based on the understanding derived from the above studies that can form the basis for developing novel ceramic coatings employing the solution precursor plasma spray technique. © 2013 Elsevier Ltd.