Promoting the spreading and deposition of agricultural sprays on the crop surface is of great significance for effective utilization of these chemicals. Selective host-guest interaction established between chlormequat and hydroxyl pillar[5]arene was well utilized in the present work for effective spreading of chlormequat droplets over the hydrophobic surface, which was silanized with triethoxy (octyl) silane and then assembled with hydroxybenzene pillar[5]arene molecules. Therefore, this surface was facile for the assembly of chlormequat in droplets and ultimately increased the selective adhesion of chlormequat through host-guest interactions. Moreover, the pillar[5]arene-fabricated surface shows considerable potential applications for rapid detection of chlormequat in environmental monitoring and also provides a novel approach for improving the chlormequat efficiency.