The optimisation process for the synthesis of microcapsules containing trioctylmethylammonium chloride (TOMAC), a selective extractant agent for the removal of mercury from wastewaters, by the suspension copolymerisation of styrene (St) and divinylbenzene (DVB) was studied. The influence of the diluent, mass ratio of the suspending agents (arabic gum -AG- and polivinylalcohol -PVA-), TOMAC:diluent volume ratio and weight percentage of DVB respect to the monomers mixture (% DVB) on the encapsulation process and the physical properties of the resulting microcapsules were investigated. It was found that using heptane as diluent led to non-spherical microcapsules with poor reaction yield and conversion of the monomers. Nevertheless, when toluene was used these properties were improved. Furthermore, for a TOMAC:toluene ratio of 1:3 spherical beads were obtained. The combined use of the suspending agents was more appropriate than using them separately, due to the latex product and the low conversion of the monomers for AG and PVA, respectively. The increase of the % DVB from 18.8 to 50% enhanced the mechanical resistance of the polymeric shell, increasing the reaction yield up to an 84.7% and maintaining the TOMAC encapsulation (36.0%) and the sphericity of the microcapsules. The obtained particle size (40 mu M) indicated that the main application of this material will be in fluidised beds or in perfectly mixed reactors. On the basis of the experimental results, a AG:PVA mass ratio of 1:1, a TOMAC:toluene volume ratio of 1:3 and 50% DVB were established. as the best conditions to produce this kind of microcapsules, enabling its reproduction on a pilot scale plant. In addition, the high values of the distribution coefficient for mercury removal confirm the success of this optimisation process. (C) 2016 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.