Part I: Single sized, pure arylene ether macrocycles ranging from 30 to 60 atom ring sizes were synthesized in good yields (up to 83%) by the two component method under high dilution conditions. These macrocycles have unsymmetric structures containing sulfone/ketone or sulfone/phosphine oxide functional groups and have relatively low melting points. The melt ROP of the single sized macrocycles to form poly(arylene ether)s exhibits two stage characteristics: the first stage is very fast, driven by the large entropy difference between cyclics and linears; the second stage is very slow and is diffusion controlled due to the high viscosity created in the first stage reaction. The latter stage leads to incomplete polymerization at the low initiator concentrations (1-3 mol%). At high initiator concentrations (5-7 mol%), 100% conversion is reached due to improved initiator distribution in macrocycles; however, this reduces molecular weights of the polymers. The molecular weight is found to build up very rapidly, independent of conversion, reaction time and type of initiator. The ROP is initiated by CsF and alkali phenoxides. The efficiency of the alkali counterion is generally in the order of Cs+>K+>Na+, while a phenoxide initiator is more efficient than a fluoride initiator. It is also found that the Cs counterion leads to highest degree of crosslinking. The ROP of cyclic oligomeric mixtures is also reported for comparison; the study shows that the molecular weight depends on time and conversion, and that the conversion is sensitive to the content of linear impurities and the average ring size of cyclic mixtures. Part II: Polyrotaxanes are novel polymeric materials comprised of linear polymer molecules and threaded macrocycles with no covalent bond between the two components. With potential movements of the cyclic component and judicious combinations of the two components of different properties, these materials have brought interesting changes of physical properties, such as morphology, crystallinity, solubility, viscosity, etc. In this part of the dissertation, a new family of polyrotaxanes with poly(arylene ether)s as backbones and crown ethers as cyclic components are described. These include linear poly(arylene ether) based polyrotaxanes and hyperbranched poly(ether ether ketone) based polyrotaxanes; both are synthesized via aromatic nucleophilic substitution reactions. Preliminary studies show that these polymers exhibit great enhancement of solubility. The polymers form emulsions in water and methanol which are normally non-solvents for the poly(arylene ether) backbones. In some cases, they are even soluble in water to form a clear solution. The attempted syntheses of polyrotaxanes using aromatic macrocycles described in Part I was not successful, with no indication of threading.Ph. D.