Processes for catalytically synthesizing ethylbenzene from ethanol and benzene comprising: 1) reacting a first mixture comprising ethanol and benzene with at least one catalyst chosen from binder-containing alkylation catalysts and binder-free alkylation catalysts in an alkylation reactor to obtain a second mixture comprising residual benzene, ethylbenzene, diethylbenzene, and water; 2) passing the second mixture successively through a benzene recovery tower, an ethylbenzene recovery tower, and a polyethylbenzene recovery tower to obtain separated water, separated benzene, separated ethylbenzene, and separated diethylbenzene; and 3) reacting a third mixture with at least one transalkylation catalyst in a transalkylation reactor, wherein the third mixture comprises at least some of the separated benzene and at least some of the separated diethylbenzene at a weight ratio ranging from about 2:1 to about 10:1.