Two porphyrin chromophores, P1 and P2, were prepared and used as antenna units to coordinate with a metal-free organic dye, JH1, containing pyridine groups. This supramolecular self-assembly strategy can not only effectively improve the light-harvesting ability of the devices but also effectively reduces electron recombination by preventing I3- of the electrolyte from penetrating into the TiO2 surface. The DSSC based on JH1 showed a PCE of 2.46%, with a Voc of 615 mV, Jsc of 6.54 mA cm-2, and FF of 61.18%. After supramolecular self-assembly, the Jsc and Voc of the device were greatly improved. Specifically for the device based on JH1 + P2, the PCE reached 4.39%, which is about 78% greater than the PCE of the device based on JH1; this is mainly due to the Jsc increase of 2.85 mA cm-2 and the Voc increase of 93 mV. Compared to co-sensitization, supramolecular self-assembly does not require tedious optimization steps; thus, this may be a promising and convenient way to improve the overall performance of DSSCs.