The behavior of alumina-supported palladium-platinum catalysts in the reaction of n-hexane hydrogenolysis was analyzed. The monometallic Pt/Al2O3 catalyst showed much higher activity than the rest of catalysts. The relationship between the catalytic activity of Pd-Pt/Al2O3 catalysts and bulk Pd-Pt composition matched the accepted relation between the surface composition and bulk composition of Pd-Pt, confirming a high surface enrichment in palladium. A linear relation between the apparent activation energy and preexponential factor (compensation effect) suggests that the reaction mechanism is similar for all Pd-Pt catalysts. However, after very high temperature of catalyst reduction (at 600 degrees C), the behavior of monometallic Pd/Al2O3 catalyst exhibited a considerable departure from the compensation plot, and drastic variations in C-1-C-5 products distribution. Such big changes are rationalized by assuming the transformation of Pd/Al2O3 into Pd-Al alloy, occurring at very high temperature of reduction. Product distribution of n-hexane hydrogenolysis for Pt/Al2O3 differs from that of Pd/Al2O3, showing more internal bond splitting than a terminal demethylation. However, bimetallic Pd-Pt/Al2O3 catalysts showed even more 'internal bond splitting' character than the Pt/Al2O3. Reasons for this synergism and changes in the behavior of Pd/Al2O3 catalysts are analyzed in terms of an electronic interaction between metals and alumina support.