Through different functionalization methods, three kinds of Rh-immobilized mesoporous silicas have successfully been prepared to investigate catalytic behavior, including yield and the linear/branched ratio of aldehyde (L/B) in 1-octene hydroformylation. A conventional post grafting method and two kinds of selective bifunctionalized methods for modification of the mesoporous silica have been applied for this purpose. A relatively high L/B (> 2.0) was effectively achieved using Rh-immobilized inner pores in the MCM-41 support due to the confinement effects of the Rh complex in the nanospace. Moreover, the Rh-immobilized MCM-41 catalyst, passivated with trimethylchlorosilane (TMCS) only on the external surface, showed fairly good yields of the aldehyde (> 40%).