The target of this work is to investigate the effect of small additions of SiO2 or CaO on the sintering behavior and the microstructure of an ultrapure α-alumina compound. The sintering behavior has been investigated through extensive dilatometric study. SiO2 additions lead to a significant decrease in shrinkage rate during the intermediate stage of sintering whereas CaO is beneficent to densification. It has been found that during this stage which corresponds to the maximum of densification rate, grain boundaries diffusion controls densification through oxygen vacancies. The study of the densification behavior under different atmospheres help us to explain the role of the additives in agreement with electroneutrality equations. S.E.M. investigations confirm the well know correlation between doping and heterogeneous microstructures. After doping with SiO2 or CaO, abnormal grain growth appears at temperatures corresponding to the lowest eutectics given by Al2O3-SiO2 or Al2O3-CaO phase diagrams. H.R.T.E.M. observations show that below the critical temperatures for abnormal grain growth, additives enrichment is observed near grain boundaries (GBs). Above these temperatures, glassy phase for SiO2-doping and calciumhexaluminate (CA6) for CaO-doping are present at grain boundaries.