Recent advances in our fundamental understanding of soft tissues and robotics have spurred a desire to create intricate, robust devices suited to a variety of applications (e.g. wound dressings, soft actuators, additive manufacturing, etc). This revolution is currently constrained by the bottleneck of contemporary soft materials available to researchers. To truly expound upon these growing research areas, the next generation of soft materials must be tailored to host unique, multifunctional properties. Such materials are realizable in the form of polymeric networks, which are ubiquitous as the basis for a large range of materials with a continuum of properties (e.g. adhesives, membranes, and structural materials). The precise, coded design of polymeric building blocks will expand the available window of materials to include those hosting the unique properties required for next-generation device fabrication. Of specific interest among such polymeric building blocks are bottlebrush networks (BBNs). BBNs contain a large array of architectural parameters that position them strongly to serve as a foundation upon which chemists may engineer desirable properties. Despite the apparent malleability of the BBN architecture, a lack of chemical diversity has severely hindered its progression as a materials platform. This shortcoming stems largely from the architecture’s origin in the physics discipline, where BBNs have historically been synthesized via radical polymerization methods using low T_g side chains (resulting in BBEs). This dissertation focuses on building out the BBN platform using the unique benefits of living polymerization methods—specifically ring-opening metathesis polymerization (ROMP). Chapter 1 details fundamental BBN knowledge, providing a solid foundation for which to build upon for the remainder of the thesis. Chapter 2 focuses almost entirely upon synthesis, in particular macromonomers and bottlebrush controls by which to gauge BBN kinetic chain lengths (R_Ks). Chapter 2 further illustrates BBN syntheses by detailing the first homopolymer BBNs synthesized with poly(ethylene glycol) [PEG]. Chapter 3 focuses on the synthesis and characterization of bottlebrush amphiphilic polymer co-networks (B-APCNs) containing both PEG and poly(dimethyl siloxane) [PDMS] side chains. Synthesized B-APCNs are shown to have tunable mechanical properties controlled by manipulating the volume fractions of either PEG or PDMS side chains, suppressing the organization of chains into discrete crystalline domains. Chapter 4 demonstrates how the level of molecular defects in BBEs synthesized via free radical polymerization and ROMP affect their mechanical properties through the development of a new parameter coined the “structural efficiency ratio”. This SER demonstrates that ROMP-based PDMS BBEs form stress-supporting strands rather ineffectively (14%) at [0.11 M] concentrations. Chapter 5 illustrates how manipulation of R_K during living polymerization impacts the structure and mechanical properties of networks, importantly introducing the concept of “network constitutional isomers” [NCIs]. These NCIs are demonstrated to have dramatically different molecular structures because of minor variations in polymerization chemistry—the amount of catalyst and type of catalyst. Chapter 6 combines insights from chapters 3-4 to build defects into BBEs—a design philosophy termed “defect-driven design” (D³)—by synthesizing ultra-low crosslink density samples. These D³ BBEs are further demonstrated to perform exceptionally well as pressure sensitive adhesives, with the hydrophobic PDMS side chains used allowing for underwater adhesion to become possible.