Self-assembly is considered to be the process through which building blocks spontaneously organize into well-defined frequently functional structures. The tailoring of properties of such structures has drawn attention in various fields, in particular, in enzymatic cascade reactions, drug delivery, amphiphilic copolymer nanocontainers, and nanoreactors. Polymer-DNA hybrid self-assemblies, in addition to responsiveness to ionic strength, are sensitive to hybridization, which renders the establishment of a theoretical framework challenging when both specific hydrogen bonding between complementary sequences and association are to be taken into consideration. Numerous various highly characterized self-assemblies are recognized to organize through nucleation dependent polymerization, including microtubule formation, sickle-cell fibril formation, flagellum assembly, among others. Interpolyelectrolyte complexes (IPECs) have attracted attention due to the large number of emerging and potential applications. Environmental factors such as the medium also play a role in the complex formation process, especially pH and ionic strength.