Rational control of catalytic selectivity still remains a grand challenge in the field of biomass conversion to valueadded chemicals. In this paper, we used PtFe catalyst as an example to understand fundamentals for lattice strain, electronic reconfiguration, reaction kinetics and catalytic selectivity for aqueous conversion biopolyols. Structurally strained face centered tetragonal (fct) PtFe crystals were synthesized and it was confirmed that such unique PtFe nanostructures display intriguing electronic coupling effect and partial charge distribution, as revealed by surface characterization using TEM, XRD and XPS, as well as DFT calculation. Bimetallic PtFe-fct catalysts exhibit a remarkable catalytic activity (TOF: 24 312 h(-1) at 65 degrees C and 1 MPa O-2), enhanced selectivity (tartronic acid: 54%) and improved stability for aqueous phase oxidation of biopolyols, in comparison with conventional fcc morphology. Kinetic modeling further indicates that relatively lower oxidation barrier and restrained decarboxylation reaction are key for improving selectivity on PtFe-fct catalysts.