This invention refers to a process for the synthesis of phenol and acetone starting from cumene hydroperoxide, and to a plant specifically developed for performing this process. More in particular, this invention refers to a process for the synthesis of phenol and acetone starting from cumene hydroperoxide, comprising the following steps: a) Pretreating of the starting cumene hydroperoxide with acidic resins, to obtain cumene hydroperoxide free of inorganic cations; b) Decomposing of the cumene hydroperoxide free of inorganic cations originating from the step (a) in the presence of acidic resins, to yield phenol and acetone.