Poly(amidoamine), a polymer with several amide and amine groups are widely explored in biomedical field as dendrimers, which are monodispersed, synthetic, three-dimensional, hyperbranched nano-polymeric structured substances that are commonly regarded as homogeneous molecules. PAMAM dendrimers, also commercially known as “Starburst” are employed widely in gene/drug delivery as well as materials of choice for several supramolecular chemistry applications. Many important biological features, including bioavailability, solubility, and selectivity, can be improved by entrapping bioactive molecules into the dendrimer frame. One of the more sophisticated uses of PAMAM is in their instructing groups to achieve selective delivery in desired organs of choice. This chapter discusses several PAMAM synthesis techniques, its surface modifications, and biomedical applications. The features of supramolecular PAMAM dendrimers in nano polymer research have been demonstrated substantially in gene transport, drug delivery, and many other applications when compared to other normal nano polymers.