Aromatic hydroxylation of pseudocumene and mesitylene with P450 BM3 yields key phenolic building blocks for a-tocopherol synthesis. Site-saturation mutagenesis generated a new P450 BM3 mutant, named “variant M3” (R47S, Y51W, A330F, I401M), with significantly increased coupling efficiency (3- to 8-fold) and activity (75- to 230-fold) for the conversion of pseudocumene and mesitylene. Here the dataset to “An Enzymatic Route to α‐Tocopherol Synthons: Aromatic Hydroxylation of Pseudocumene and Mesitylene with P450 BM3” (Alexander Dennig, Alexandra Maria Weingartner, Tsvetan Kardashliev, Christina Andrea Müller, Erika Tassano, Martin Schürmann, Anna Joëlle Ruff, Ulrich Schwaneberg, Chemistry. 2017 Dec 19;23(71):17981-17991., doi: 10.1002/chem.201703647) is given. This study provides an enzymatic route to key phenolic synthons for a-tocopherols and the first catalytic and mechanistic insights into direct aromatic hydroxylation and dearomatization of trimethylbenzenes with O2.Source data of the performed substrate docking, and mechanistic considerations are given. Docking of mesitylene into the active site of P450 BM3 WT (source data to Fig1) and the homology model of P450 BM3 variant M3, as well as Docking of pseudocumene into the active site of P450 BM3 WT (1BU7) (source data to Fig2) and P450 BM3 variant M3 (R47S, Y51W, A330F, I401M) (source data to Fig3) are submitted. In the description of dataset a summary of the docking source data is given