Here, we show that Au nanoparticles having diameters of less than 2.2 nm can be extracted from within the interior of PAMAM dendrimers using n-alkanethiol extractants. Extraction proceeds quickly, regardless of the size of the nanoparticle, the dendrimer generation, or the peripheral functionalization of the dendrimer. The extraction rate is fastest for the lowest generation dendrimers, the smallest nanoparticles, and the shortest chain-length n-alkanethiols. Other important results of this study include the following. First, within the accuracy of absorbance spectroscopy, the extraction yield is quantitative. Second, NMR and FT-IR spectroscopy indicate that after extraction the dendrimer remains in the aqueous phase and can be used to template additional metal particles. Third, the size and optical characteristics of the extracted nanoparticles are the same as the precursor dendrimer-encapsulated nanoparticles (DENS). Fourth, a 100-fold excess of n-alkanethiol molecules is required to prevent aggregation of DENS during extraction.