We have selectively hydrophobized halloysite nanotube lumens for efficient loading with a flame retardant for controlled releasing composite materials. The inner lumen of octadecylphosphonic-acid-modified halloysite was loaded with hydrophobic bisphenol-A bis(diphenyl phosphate). This flame retardant was released from the clay nanotubes in linear fashion over 60 h demonstrating the system potential utility as effective nanocontainers for smart composite systems.There has been considerable interest in materials based on aluminum silicate nanotubes because of their unique features and applications. 13 Halloysite nanotubes (HNTs) are naturally occurring aluminum silicate hollow cylinders with a length of 0.51¯m, the outer and inner diameters of ca. 3050 and 10 30 nm, respectively.3 High loading efficiency of the halloysite nanotubes is related to efficient adsorption of drugs into positively charged HNTs' inner lumen, 4,5 using a variety of solvents 6 and polarity differences of the adsorbent and adsorbate. 7 Halloysite can be selectively modified to achieve the hydrophobicity of its inner surface.3,7 Bisphenol-A bis(diphenyl phosphate) (BDP) is known to be one of the most effective nonhalogenated, environmentally benign flame retardants. 8,9 However, due to the weak interaction between rather hydrophobic BDP and hydrophilic inner surface of the pristine halloysite tubes, it is difficult to achieve its high loading efficiency. Recently, we reported a novel selective modification for the inner lumen of halloysite with octadecylphosphonic acid (ODP), based on strong specific interaction between the phosphonic acid group and aluminol groups of the clay inner lumen.3 Here we report the high loading and controlled release of bisphenol-A bis(diphenyl phosphate) into the ODP-modified halloysite tubes (Scheme 1).The selective ODP grafting on the surface of inner lumens of halloysite was carried out by pulling and breaking vacuum. The BDP was sorbed in the ODP-modified halloysite nanotubes (HNTs-ODP) by adding a saturated ethanol solution of BDP to a suspension of HNTs-ODP and stirring the mixture for one week. The suspension was centrifuged, and the precipitate was dried at 393 K under ambient pressure for 10 h resulting in the final formulation: HNTs-ODP-BDP. Figure 1 shows the nitrogen adsorptiondesorption isotherm of HNTs, HNTs-ODP, HNTs-BDP, and HNTs-ODP-BDP at 77 K. Corresponding surface area (S BET ), pore volume (V pore ), and pore size (d peak ) are listed in Table 1. The samples were dried at 373 K for 30 min and outgassed under vacuum at 373 K flame retardant(BDP)