Demands related to clean energy and environmental protection promote the development of novel supramolecular assemblies for photocatalysis. Because of the distinctive aggregation behaviors, bolaamphiphiles with two hydrophilic end groups could be theoretically the right candidates for the fabrication of high-performance photocatalysis. However, photocatalytic applications based on bolaamphiphilic assemblies were still rarely investigated. Especially, the relationship between diverse assembled nanostructures and the properties for different applications is urgently needed to be studied. Herein, we demonstrate that using the hierarchical assembly of bolaamphiphiles could correctly induce the porphyrin supramolecular architectures with much better photocatalytic performances than the aggregations containing 450 times of the porphyrin molecules, even though both molecular structures as well as the J-aggregations of porphyrin building blocks are same in two different systems. Thus, the co-assembly of l -phenylalanine terminated bolaamphiphile (Bola-F) and the porphyrin containing four hydroxyl groups (tetrakis-5,10,15,20-(4-hydroxyphenyl)porphyrin) can form microtube in methanol and forms fibers/spheres in methanol/water mixture. For catalyzing the photodegradation of rhodamine B, the small amount of J-aggregated porphyrin within Bola-F microtubes show much better photocatalytic performance comparing with that of huge porphyrin J-aggregations in fibers/spheres. The supramolecular assemblies as well as the photocatalysis were thoroughly characterized by different spectroscopies and electron microscopy. It is demonstrated that the co-assembly with bolaamphiphiles could inhibit the energy transfer of porphyrin aggregation and subsequently benefit the electron transfer and corresponding photocatalysis under photo-irradiation. This work is not only useful for further understanding the hierarchically supramolecular assembly but also provides a new strategy for making novel functional supramolecular architectures based on the assembly of bolaamphiphiles and porphyrins.