Selective modification of the inner surface of halloysite nanotubes (HNTs) by the cycloaddition of azides and alkynes (click reaction) was successfully achieved. Fourier transform infrared spectroscopy and thermogravimetry confirmed that the modification involved only the HNT cavity. Morphological investigations evidenced that the functionalized nanotubes formed microfibers and clusters in the micrometer range. By means of the casting method, these nanomaterials were dispersed into biopolymeric matrixes (chitosan and hydroxypropyl cellulose) with the aim of obtaining nanocomposite films with tunable properties from the physicochemical viewpoint. For comparison purposes, we also characterized composite nanomaterials based on pristine halloys...