The understanding of ash sintering during combustion of agricultural residues is far from complete, because of the high heterogeneity of the content and composition of ash forming matters and the complex transformation of them. In order to make agricultural residues competitive fuels on the energy market, further research efforts are needed to investigate agricultural residues' ash sintering behavior and propose relevant anti-sintering measures. The aim of this work was to investigate the ash characteristics of rye straw and effects of additives. Three additives were studied regarding their abilities to prevent and abate rye straw ash sintering. Standard ash fusion characterization and laboratory-scale sintering tests were performed on ashes from mixtures of rye straw and additives produced at 550°C. Ash residues from sintering tests at higher temperatures were analyzed using a combination of X-ray diffraction (XRD) and scanning electron microscopy-energy dispersive X-ray spectrometry (SEM-EDX). High sintering and melting tendency of the rye straw ash at elevated temperatures was observed. Severe sintering of the rye straw ash was attributed to the formation and fusion of low temperature K-silicates and K-phosphates with high K/Ca ratios. Among the three additives, calcite served the best one to mitigate sintering of the rye straw ash. Ca from the calcite promoted formation of high temperature silicates and calcium rich K-phosphates. In addition, calcite may hinder aggregating of ash melts and further formation of large ash slag. Therefore, the chemical reactions and physical restraining effects arose by calcite addition contributed to reduction of ash melts and sintering degree. Upon addition of kaolin, compositions of rye straw ash shifted from low temperature melting K-silicates to high temperature melting K-Al-silicates. The changes of ash chemistry were favorable for reducing sintering of the rye straw ash. As the Ca-sludge was added, reduction of sintering of the rye straw ash was less pronounced. Only K4CaSi3O9 and a small amount of KCaPO4 were identified in the rye straw ash as Ca-sludge was added. © 2015 Elsevier Ltd.