In this paper the optimization of the kaolin calcination is studied, aiming at using the produced metakaolin as supplementary cementitious material. Representative samples of poor Greek kaolin (Milos island) and a high purity commercial kaolin were tested. Samples were heated at different temperatures during different times. The optimization of calcination conditions was studied by DTA-TG and XRD analysis of the raw and thermal treated kaolin samples, by pozzolanic activity analysis of metakaolins and finally by strength development analysis of cement-metakaolin mixtures. This approach showed that heating at 650°C for 3 h is efficient to convert poor kaolins with low alunite content to highly reactive metakaolins. However in the case of kaolin with a high alunite content, thermal treatment at 850°C for 3 h is required in order to remove undesirable SO3. Evidence was found that poor kaolins can be efficiently used for the production of highly reactive metakaolins.