In this paper, we applied the SGD approach to the design of selective oxidation phosphorus-containing supported catalysts based on data from HTE and DFT calculations. The yield of valueadded oxygenate product measured by HTE was used as target, and parameters obtained from DFT-calculated free-atom properties were offered as candidate descriptive parameters. The composition-weighted electronegativity, the phosphorus content and the temperature are identified as key parameters associated to outstanding production of acrolein and acrylic acid from propylene in three-component catalysts containing ruthenium, tungsten and phosphorus. The SG rules on these key parameters not only rationalize a local reactivity pattern particularly associated with exceptional catalytic performance, but also guide the design of more complex catalysts. In particular, a five-component material containing ruthenium, tungsten, phosphorus, tellurium and tantalum in the composition, which presents an oxygenate yield more than twice as large as any observation in data set used for training, is captured by the SG rules. This local modelling approach is suitable for the search of exceptional materials whose structures and functions are hardly modelled explicitly by theory.