Ethyl-octyl ether (EOE) liquid phase synthesis from ethanol and 1-octanol over ion-exchange resins is feasible at 423K, though di-ethyl ether and di-n-octyl ether were also formed. The influence of the catalyst morphology on the reaction was checked by testing twenty-two acidic resins. Gel-type resins of low crosslinking degree yielded the higher amounts of EOE, whereas macroreticular ones of high crosslinking degree gave mainly di-ethyl ether. Ethanol conversion highly depends on the resin acid capacity, [H+], whereas 1-octanol conversion and selectivity to EOE depends on the specific volume of swollen polymer, Vsp, and porosity. The variation of ethanol and 1-octanol conversion, selectivity to EOE with respect to both alcohols as well as ethers TOF as a function of [H+]/Vsp suggests that a part of the active sites does not take part in the EOE synthesis reaction on highly cross-linked resins. Amberlyst 70 could be interesting in industry due to its selectivity to EOE and higher thermal stability