Metal-free porphyrin with good planarity is beneficial to π-π stack interactions, which promotes electron coupling and the separation and transfer of photogenerated carriers. It is necessary to develop metal-free porphyrin-based photocatalysts and exploit the photocatalytic mechanism. Herein, metal-free porphyrin (5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin, TCPP) was self-assembled through an acid-based neutralization reaction and mixing dual-solvents under surfactants to form different aggregates. Morphology structures, optical and optoelectronic properties of the TCPP aggregates were characterized in detail. TCPP self-assemblies showed higher photocatalytic activities for the degradation of phenol under visible light than untreated TCPP powders, and the aggregates of nanorods formed through the acid-based neutralization reaction in the presence of hexadecyl trimethyl ammonium bromide (CTAB) possessed 2.6 times more activity than the nanofiber aggregates formed through mixing dual-solvents. It was proved that self-assembly methods are crucial for controlling the aggregation of porphyrins to form different aggregations, which have a profound impact on the photocatalytic activity.