The objective of this study is to determine the mechanism of mercury retention in fly ashes, the main solid waste from coal combustion power plants, and to evaluate the interactions between the type of mercury and fly ashes. The work was based on the results of mercury speciation in the gas and the solid fly ash before and after mercury retention. The identification of the mercury species in the gas was performed using previously validated methods, but the speciation of the mercury retained in the fly ashes was carried out using a mercury temperature-programmed desorption technique (HgTPD) still under development. The fly ashes were sampled from conventional coal combustion in air and oxy-combustion power plants. The main mercury species identified in the raw fly ashes and after they were subjected to an oxy-combustion atmosphere were mercury bound to organic matter and HgS, the ratio of these species depending on the characteristics of the ashes. The results obtained indicate that fly ashes are the route of mercury oxidation in an oxy-combustion atmosphere, although they hardly retain any mercury unless the unburned carbon content is high. HgTPD analysis shows that the main mechanism for mercury retention in the fly ashes is via the carbon matter. The financial support for this work was provided by the National Research Program under project CTM2011–22921. The authors thank CIEMAT (Department of Energy) and CIUDEN for supplying the fly ashes employed in this study, PCTI Asturias for awarding Ms. Nuria Fernandez-Miranda a pre-doctoral fellowship and the Spanish Research Council (CSIC) for awarding Ms. Marta Rumayor a JAE-predoc fellowship. Peer reviewed