Polyhomologation is a powerful method to prepare polyethylene-based materials with controlled molecular weight, topology and composition. This dissertation focuses on the discovery of new synthetic routes to prepare polyethylene-based macromolecular architectures by combining polyhomologation with highly orthogonal and efficient linking reactions such as Diels Alder, copper-catalyzed azide-alkyne cycloaddition (CuAAC), and Glaser. Taking advantage of functionalized polyhomologation initiators, as well as of the efficient coupling chemistry, we were able to synthesize various types of polymethylene (polyethylene)-based materials with complex architectures including linear co/terpolymers, graft terpolymers, and tadpole copolymers. In the first project, a facile synthetic route towards well-defined polymethylene-based co/terpolymers, by combining the anthracene/maleimide Diels–Alder reaction with polyhomologation, is presented. For the synthesis of diblock copolymers the following approach was applied: (a) synthesis of α-anthracene-ω-hydroxy-polymethylene by polyhomologation using tri (9 anthracene-methyl propyl ether) borane as the initiator, (b) synthesis of furan-protected-maleimide-terminated poly(ε-caprolactone) or polyethylene glycol and (c) Diels–Alder reaction between anthracene and maleimide-terminated polymers. In the case of triblock terpolymers, the α-anthracene-ω-hydroxy polymethylene was used as a macroinitiator for the ring-opening polymerization of D, L-lactide to afford an anthracene-terminated PM-b-PLA copolymer, followed by the Diels–Alder reaction with furan-protected maleimide-terminated poly (ε-caprolactone) or polyethylene glycol to give the triblock terpolymers. The synthetic methodology is general and potentially applicable to a range of polymers. The coupling reaction applied in the second project of this dissertation was copper-catalyzed “click” cycloaddition of azides and alkynes (CuAAC). Novel well-defined polyethylene-based graft terpolymers were synthesized via the “grafting onto” strategy by combining nitroxide-mediated radical polymerization (NMP), polyhomologation and copper(I)-catalyzed azide–alkyne cycloaddition (CuAAC). Three steps were involved in this approach: (a) synthesis of alkyne-terminated polyethylene-b-poly(ε-caprolactone) (PE-b-PCL-alkyne) block copolymers (branches) by esterification of PE-b-PCL-OH with 4-pentynoic acid; the PE-b-PCL-OH was obtained by polyhomologation of dimethylsulfoxonium methylide to afford PE-OH, followed by ring opening polymerization of ε-caprolactone using PE-OH as a macroinitiator (b) synthesis of random copolymers of styrene (St) and 4-chloromethylstyrene (4-CMS) with various CMS contents, by nitroxide-mediated radical copolymerization (NMP), and conversion of chloride to azide groups by reaction with sodium azide (NaN3) (backbone) and (c) “click” linking reaction to afford the PE-based graft terpolymers. This method opens up new routes for the creation of polyethylene-based graft terpolymers by a combination of polyhomologation, NMP and CuAAC. The third project deals with the synthesis of polyethylene-based tadpole copolymer (c-PE)-b-PSt. Cyclic polymers represent a class of understudied polymer architecture mainly due to the synthetic challenges. Within this dissertation, a new method was reported for the synthesis of cyclic polymers in exceptionally high purity and yield. The main approaches to synthesize macrocycles are based on the end-to-end ring-closure (coupling) of homo difunctional linear precursors under high dilution. Our process relies on the preparation of well-defined linear α, ω-dihydroxy polyethylene and a bromide group at the middle of the chain through polyhomologation of ylide using functionalized initiator, followed by ATRP of styrene monomer. The two hydroxyl groups were transformed into alkyne groups, via esterification reaction, followed by Glaser reaction between terminal alkynes to afford the tadpole-shaped copolymers with PE ring and PSt tail. In Our PhD research, we also studied the self-assembly properties of the amphiphilic copolymers PM-b-PEG in aqueous solution by DLS, Cryo-TEM, and AFM. Furthermore, the critical micelle concentration (CMC) was estimated from the intensity of the pyrene emissions by the fluorescence technique. All the findings presented in this dissertation are emphasizing the utility of polyhomologation for the synthesis of well-defined polyethylene-based complex macromolecular architectures, almost impossible through other kind of polymerization including the catalytic polymerization of ethylene.