Porous hollow silica nanoparticles (PHSNs) were prepared and applied as controlled delivery system of water-soluble pesticide validamycin. PHSNs were loaded with validamycin through a specially designed supercritical fluid loading method. It was demonstrated that a high loading capacity (36 wt.%) of validamycin could be achieved, which was found to be more effective than that of the simple immersing method in this study. The loaded PHSNs were characterized by TG, IR and XPS analysis. The validamycin release profile from PHSNs was investigated and showed a multi-staged release pattern probably due to the different adsorption locations of validamycin on PHSNs. This release behavior makes PHSNs a promising carrier in agriculture, especially for pesticide controlled delivery whose immediate as well as prolonged release is needed. In addition, factors influencing the validamycin release rate, including pH and temperature, were investigated. (C) 2006 Elsevier Ltd. All rights reserved.