A series of tricarbonyl Re(V) complexes i.e. [Re(CO)3(κ3-PN2)] 1, [Re(CO)3Br(κ2-H2PNO)], 2 and [Re(CO)3Br(κ2-HPN-Pip)], 3 have been covalently anchored over modified SBA-15 as supported catalysts. Remarkably, high catalytic turnover numbers from 2240 to 2857 with high ketone selectivity was obtained for both C5 and C6-alkanes. Best oxidation condition was optimized by the variation of temperature, pressure, time and catalyst amount. A thermal stability tests indicates that the catalysts are stable up to 200 ºC and ICP shows negligible metal loss from the catalyst surface, after the 7th catalytic cycle, allowing further use.