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Abstract Herein, we probe the hydrogen bond‐driven self‐assembly of a triphenylamine (TPA) bis‐urea macrocycle in the presence and absence of guests. Comprised of methylene urea‐bridged TPAs with exterior tridodecyloxy benzene solubilizing groups, the macrocycle exhibits concentration‐dependent aggregate formation in THF and H₂O/THF mixtures as characterized by¹H NMR and DOSY experiments. Its assembly processes were further probed by temperature‐dependent UV/Vis and fluorescence spectroscopy. Upon heating, UV/Vis spectra exhibit a hypsochromic shift in the λ_max, while fluorescence spectra show an increase in emission intensity. Conversely, the protected macrocycle that lacks hydrogen bond donors demonstrates no significant change. Thermodynamic analysis indicates a cooperative self‐assembly pathway with distinct nucleation and elongation regimes. The morphology and structure of the aggregate were elucidated by dynamic light scattering, atomic force microscopy, scanning and transmission electron microscopy. Variable temperature emission spectra were utilized to monitor the impact of guests, such as diphenylacetylene, that can be bound in the columnar channels. The findings suggest that the elongation of assemblies is influenced by the presence of these guests. In comparison, diphenyl sulfoxide, likely functioning as a chain stopper, limited the assembly size. These studies suggest that judicious selection of (co)monomers may modulate the function and utility of these supramolecular systems.