In this paper, sodium alginate crosslinked porous silica carrier (SA-SiO2) was introduced by one-pot co-condensation method, and Cu2+ was adsorbed on the carrier by –COOH to in-situ synthesized composite materials (HKUST-1@SA-SiO2). A series of characterizations were carried out by FT-IR, BET, XRD, XPS, SEM, and TEM. The results showed that the carrier SA-SiO2 was successfully cross-linked, HKUST-1 was successfully surface functionalized and the composites was spongy with pores. The catalytic activity and reusability of the compound HKUST-1@xSA-SiO2 were investigated for the reduction of 4-nitrophenol to 4-aminophenol. Among them, HKUST-1@0.15SA-SiO2 had the best catalytic performance and the conversion rate constant was 0.45 min−1, which was better than that of the post-synthesis method. Its catalytic activity did not decrease significantly after five cycles.