In this report, we describe the synthesis of two porphyrin-containing Pt(II) supramolecular assemblies via coordination-driven self-assembly. X-ray crystallographic analysis on one assembly reveals that the metalla-assembly formation imposes large interchromophore distances, leading to a higher 1O2 generation efficiency, relative to the corresponding small molecular precursors. The metalla-assemblies were examined as photosensitizers for photodynamic therapy as the potential reduction of the unfavorable self-aggregation phenomenon. In vivo and in vitro investigations demonstrate that the metalla-assemblies exhibit enhanced anticancer activity with minimal dose requirement and side effects comparable to the small molecule precursors. Thus, our work demonstrates that self-assembly provides a promising methodology for enhancing the therapeutic effectiveness of anticancer agents.