Polymers play an important role in the advancement of materials for use in cutting-edge applications. A direct consequence of an increased demand for more sophisticated materials has been a drive toward developing polymers that exhibit a higher level of structural control, especially in terms of the number and type of functionalities provided within the polymer framework. A family of polymers that meets such a challenge is based on the readily available AB2 monomer 2,2-bismethylolpropionic acid (bis-MPA) building block. Due to the ease with which the monomers can be synthesized, an array of multifunctional polymers have been produced including monodisperse dendrimers and dendrons and well-defined linear polymers as well as linear-dendritic hybridizations. This review outlines the evolution of the synthetic strategies for developing novel polymeric architectures based on bis-MPA and their assessment in both solution and substrate-based innovative applications.