Nowadays, the over use of antibiotics has led to the production of biofilms, which cause antimicrobial treatment to fail and thus are a severe threat to public health globally. Therefore, exploiting antibiofilm agents is highly urgent. In the present study, we report an assembly that is rationally constructed by biogenic amine spermine (Spm) and molybdenum (Mo)-containing polyoxometalate clusters (Mo 154 ), which present efficient antibiofilm and bactericidal effects. On the one hand, the assembly of Mo 154 /Spm produces large aggregates, which favors 808 nm absorption and exhibits an improved photothermal transition (PTT) under near-infrared (NIR) irradiation. On the other hand, the assembly with Spm enhanced Mo 154 uptake to both the biofilm and bacteria, which improved both biofilm elimination and antibacterial effects. Therefore, in addition to providing an efficient antibacterial agent of Mo 154 /Spm assembly, the present study also offers guidance on the future design of hybrid antibacterial assemblies with efficient effects.