The synthesis of ethyl octyl ether (EOE) from a mixture of diethyl carbonate (DEC) and 1-octanol (1:2 molar ratio) over several solid catalysts was studied in batch mode at 150 degrees C and 25 bar. Catalyst screening revealed that EOE could be successfully obtained over some acid catalysts. In particular the highest yield was achieved over acid ion-exchange resins (33% after 8 h). A reaction scheme of the process is proposed. Selectivity to EOE was mainly affected by the production of diethyl ether (DEE) and di-n-octyl ether (DNOE). However, EOE was the main ether obtained (60 mol%), followed by DEE (20 mol%) and DNOE (20 mol%). By comparing the behavior of several acid resins, it was seen that the synthesis of EOE was highly related to the structural resin properties. It was found that the accessibility of DEC and 1-octanol to acid centers was improved over highly swollen and low polymer density resins. Thus, gel-type resins with low divinylbenzene content are the most suitable to produce EOE (e.g., Amberlyst 121, Dowex (R) 50Wx2-100 and CT224). (C) 2011 Elsevier B.V. All rights reserved.