Mechanically enhanced supramolecular carbon nanotube (CNT) films were prepared in water by employing the π-electronrich phenyl, naphthalenyl, and pyrenyl end-functionalized polyethylene oxides (PEOs) as supramolecular linkers, followed by vacuum filtration. Among them, the supramolecular CNT film produced by the pyrenyl end-functionalized PEO (PEOPy) exhibited the highest mechanical strength, which was ~ 1.5–2 times higher than that of the CNT films produced using the typical dispersant, Triton X-100, although the functionality of PEO-Py was lower than that prepared using other linkers, and the content of PEO-Py in the CNT films was lower than that obtained using Triton X-100. Fluorescence and UV–Vis spectroscopy demonstrated that the improved mechanical properties of the supramolecular CNT film result from the formation of π–π interactions between the CNT and the pyrene moieties of the PEO-Py linker. Finally, the supramolecular CNT film exhibited a 40–50 dB electromagnetic shielding efficiency through hybridization with silver nanowires.