In this Article, TS-1 was successfully synthesized on carbon nanotubes decorated nickel foam via in situ strategy forming the monolithic TS-1 (MTS-1). To the best of our knowledge, situ synthesis of the MTS-1 has not been reported. Carbon nanotubes decorated nickel foam has many aggregated pores (confined pores formed in aggregated structure) and a large surface area, and TS-1 particles could be dispersed on the surface of CNT@NF. MTS-1 had the characteristics of ultrafine nanoparticle and high content of skeleton titanium. High absorptive property and electrostatic interaction between CNT@NF and gels could accelerate the crystallization rate. The TS-1 particles were solidly immobilized on the CNT@NF, and the conversion rate was almost constant even after multiple reactions. The catalyst is easy to separate from liquid products after reaction, which offers an economical application prospect.