Pure benzene is an important chemical feedstock, and coking benzene is one of its sources. However, the industrialized coking benzene refining processes are not green and sustainable. To solve this problem, a green two-step process for the desulfurization of coking benzene with the advantages of easy operation, low environmental pollution and solid waste (sorbent/thiophene) recyclability was evaluated. The thiophene in coking benzene was first alkylated by the olefins present in it using a suitable AlCl3/silica gel catalyst to produce alkylthiophenes, which can be easily separated by distillation. The AlCl3/silica gel catalyst obtained by a novel green process was effective in catalyzing the alkylation of thiophene by 1-hexene with an efficiency of removing thiophene up to 94.2%. AlCl3 was grafted onto silica gel by reacting with hydroxyls on its surface, which could prevent the dissolution problem of AlCl3 in benzene. The residual thiophene with its concentration range of 100–1000 mg L−1 in benzene was then almost completely removed by adsorption using an ion-exchanged zeolite. The CeY zeolite sorbent showed excellent performance in deeply removing the residual thiophene in the benzene, in which the adsorption desulfurization over the CeY sorbent fits a Langmuir isotherm. The product met the requirements for a chemical feedstock, in that no thiophene was measured in the purified benzene by gas chromatography with a flame photometric detector. The CeY zeolite with adsorbed thiophene was used to prepare polythiophene–CeY composites by chemical oxidative polymerization using anhydrous FeCl3 as an oxidant at 0 °C. The decomposition temperature of the polythiophene–CeY composites is 480 °C, which is 60 °C higher than that of polythiophene. [ABSTRACT FROM AUTHOR]