An anionic water-soluble [2]biphenyl-extended-pillar[6]arenes modified with eight ammonium salt ions (AWBpP6) was successfully synthesized to establish a drug-drug conjugate supramolecular nanoprodrug (SNP) with a high drug-loading capacity. This SNP can generate a synergistic triple therapeutic effect of photodynamic therapy (PDT), photothermal therapy (PTT), and chemotherapy (CT; i.e., PDT-PTT-CT) with excellent biocompatibility.