Silica-supported catalysts based on Keggin-type heteropolyacids (HPAs) containing rubidium or cesium as counter cations have been prepared by the impregnation method and evaluated in the selective oxidation of isobutane to methacrolein and methacrylic acid. The catalysts were characterized by various techniques such as XRD, N2 physisorption, TGA, Raman spectroscopy, H2-TPR, and NH3-TPD in order to study their thermal stability, structural, and textural properties, acidity and reducibility. It was evidenced that the reducibility of the Keggin type HPAs was improved by supporting the active phase on SiO2. A loading of 40 wt% was the optimum for the selective oxidation of isobutane (IBAN) to methacrylic acid (MAA). The selectivities to MAA and methacrolein (MAC) at given conversion were increased when Cs+ was used as counter cation compared to Rb+. The same trend was observed for mono- and di-vanado-substituted phosphomolybdic acid, whereby the performance followed the order: CsV1/SiO2 > RbV1/SiO2 > CsV2/SiO2 > RbV2/SiO2. The density of acid sites was correlated to the catalytic activity, which underlines the importance of the acid sites for alkane activation.