p-Sulfonatocalix[4]arene-carbon nanotube (SC4-CNT), p-Sulfonatocalix[4]arene-thermally reduced graphite oxide (SC4-TRGO), p-Sulfonatocalix[4]arene-carbon nanotubes-thermally reduced graphite oxide (SC4-CNT-TRGO) are successfully synthesized by a simple chemical wet method. The obtained samples are characterized by using scanning electron microscopy, Fourier transform infrared spectroscopy, chronocoulometry, electron dispersive X-ray spectroscopy, cyclic voltammetry, and electrochemical impedance spectroscopy. The results confirmed that SC4 molecules are effectively loaded on the surface of CNT-TRGO composite compared to CNT and TRGO. The SC4-CNT-TRGO composite exhibits the highest supramolecular recognition of tyrosine and consequently excellent electrochemical response to the probe molecule compared to the other samples.