Heterogeneous alkylation of arene and related catalysis are overviewed from industrial and academic aspects. We first discuss, principally from industrial aspects, the synthesis of ethylbenzene (EB) and cumene (IPB) by the alkylation of benzene using alkene over zeolites. It targets how to get high selectivity for EB and IPB by using low ratios of alkene and benzene. The second topics we discuss are on synthesis of p-xylene by the isomerization of xylene isomers, disproportionation of toluene to p -xylene (TDP), and toluene methylation. We focus on how high selectivity is achieved during catalysis. We also discuss the alkylation of naphthalene (NP) and biphenyl (BP) over zeolites principally from academic aspects. For the selective synthesis of the slim isomers, it is important to have the slim transition state through the steric restriction by zeolite channels. Otherwise, the selectivity of the products is governed by the kinetic control to yield bulk isomers and/or by the thermodynamic control to yield the thermodynamically stable isomers. To sum up, we discuss the alkylation of arene, particularly from the point of how the zeolite channels work for shape-selective formation of the least bulky isomers. The alkylation of benzene with long-chain alkenes over zeolites is also summarized.