A series of p-alkoxylbenzamides featuring a long alkyl chain have been synthesized and are readily to form stable gels in a variety of organic solvents. Their self-assembly properties and structure-property relationship were investigated by scanning electron microscopy, X-ray diffraction, H-1 nuclear magnetic resonance, and Fourier transform infrared spectroscopy. The gels formed were multi-responsive to environmental stimuli such as temperature and fluoride anion. The results show that a combination of hydrogen bonding, pi-pi stacking and van der Waals interaction result in the aggregation of p-alkoxylbenzamides to form three-dimension networks, depending on the length of the long alkyl chain.