To develop new catalyst for controlling NO emission is important for pollution control. The investigation of NO or CO adsorption could contribute the fundamental understanding the reaction mechanism of de-NOx process and the coordinate state of the specific catalyst. Nanoporous nickel phosphate VSB-5 is an attractive catalyst and is firstly employed as the active component for the adsorption of NO and/or CO. In situ FT-IR and temperature programmed desorption (TPD) are used to characterize the adsorption behaviors. A large amount of NO and/or CO can be adsorbed in the pores of VSB-5 and strong bands from different adsorbed species are observed by in situ FT-IR investigation, which is confirmed by isotopic labeled adsorption. The amount of adsorption at room temperature unusually increases by raising the adsorption temperature to 100-200 degrees C. The possible reason may be explained by the generation of more active sites at elevated temperature which plays a more important role than corresponding desorption. The adsorption of CO and NO is competitive and the adsorbed CO may be replaced by NO due to a stronger bonding strength of the latter. This report contributes to monitor the active sites in the pores of VSB-5 and also makes VSB-5 to be an active candidate for NO or CO related catalytic process. (C) 2015 Elsevier B.V. All rights reserved.