Photocatalysts were applied to photocatalytic oxidation of propane in a fixed bed how reactor. Titanium dioxide exhibited fairly high activity but the deep oxidation was predominant. Silica-supported vanadium oxide (VS) favors the partial oxidation to form propanone and variety of aldehydes and the fast deactivation took place accompanied by reduction of vanadium ions. On the other hand, alkali-ion-modified VS exhibited the highest activity and high selectivity to propanone. The activity was stable because vanadates in alkali-ion-modified VS do not change their structure or are not poisoned by water molecules throughout the reaction. The cleavage of C=C double bond to form aldehydes predominantly proceeded in the case of photo-oxidation of l-butene over VS while in the case of photo-oxidation of Rb-modified VS, the oxidation of secondary carbon atom to form methyl vinyl ketone is favored. Methyl ethyl ketone was produced at a steady rate over Rb-VS in the photo-oxidation of n-butane. (C) 2000 Elsevier Science B.V. All rights reserved.