Selective catalytic reduction (SCR) is a well-proven method to reduce NO emission. However, to choose the right catalyst that provides a surface for reaction between NO and ammonia at low temperatures is a challenging task for a catalysts developers. In an earlier study, we prepared V2O5-CeO2-SiO2 catalyst with increasing V2O5 content by sol-gel route and found that the catalytic activity improved with increasing the V2O5 loading up to 0.5%. The catalytic activity, however, dropped when V2O5 loading was about 1% and increased back when the loading of V2O5 was about 5%. In this study, we looked into the microstructural relationship to explain these findings. The microstructures of the catalysts before and after exposure to NO gas revealed that the catalysts with 0.2% and 0.5% V2O5 were more porous after the reduction process possibly due to improved breakdown of (NH4)HCO3 to NH3 by the possible interaction with the V2O5 and CeO2-containing catalysts which consequently resulted in a more efficient NO reduction to N2 and H2O at low temperature. The microstructure of the catalyst with 1% V2O5 content to 5%, improved back the efficiency although clogging by CeVO4 phase still possible due to its presence based on XRD. The well-ordered micropores before exposure to NO and the more efficient breakdown of (NH4)HCO3 could have contributed to increase back the catalytic activity at low temperature.