To predict the agglomerate diameter formed by nano-sized Titania powders (P25) in emulsion region of annular fluidization bed photocatalytic reactor (AFBPR), a kinetic model was developed based on an assumption of a target molecule only reacts on the active site of an agglomerate in illumination field. The results indicated that the agglomerate diameter was a function of bed voidage and gas velocity for a given photocatalytic oxidation. It was obvious that the agglomerate diameter decreased with increasing bed voidage, and decreased along the heighten of fluidized bed, which were confirmed by the experimental results. The agglomerate size decreased with gas velocity increased, validated by the estimated data of force model. Finally, the veracity of kinetic model was validated by variation of gaseous compound types and their concentrations, which suggested that this kinetic model was feasible for photocatalytic oxidation of gaseous pollutants. This investigation highlights the novel method to describe the relationship between agglomerate diameter distribution formed in emulsion region of AFBPR and photocatalytic reactivity.