This article reviews the literature of the last ten years, on the operational risk in alkylation units with hydrofluoric acid for the production of gasoline with higher octane rating and clean combustion. It is presented, the technology implemented in the most modern oil refinery in Colombia. The objective is to provide useful information on the state of the art in this area of knowledge, presenting a frame of reference on the risk associated with the use of a highly corrosive catalyst such as hydrofluoric acid, which can affect the health of workers in whose case can be fatal, the operations or failures in the alkylation systems and the metallurgy of the equipment. For this purpose, the exploration of the scientific production of well-known institutions, repositories of national universities, specialized journals, patents in free databases, as well as Access to Conpes documents, institutional reports, HAZOP, among other sources of information was used, reports of accidents and occupational diseases available on the network were also reviewed. The most important conclusions of this review process show the need to implement the necessary controls to reduce the risk of exposure to this acid in oil refining plants