The presented work is focused on the design of (bio)functional materials from naturally occurring macrolactones. Enzymatic ring opening polymerization of such monomers affords aliphatic polyesters with promising material properties including biocompatibility, biodegradation and good mechanical properties. A drawback of these, as well as most aliphatic polyesters, is the lack of functionality, which is a potential hurdle to open biomedical applications in which the materials play a more active and possibly dynamic role. The primary aim of this thesis is the development of a methodology to introduce various functional groups to linear unsaturated poly(globalide) by utilizing thiol-ene coupling reactions as a post-polymerization modification. Secondly, this methodology should allow the design of three-dimensional materials, which can be bioconjugated. This includes for instance functional cross-linked films produced by thiol-ene coupling reactions and subsequent thiol-ene functionalization and well as exploring surface initiated ARGET-ATRP in order to increase the density of surface functional groups. Beyond the development of chemical routes it is the aim of the thesis to provide a first proof of concept for the feasibility of the developed approaches to design advanced biomaterials by investigating the conjugation with biomolecules. Moreover, first evidence for the processibility into the more complex three-dimensional materials such as scaffolds and particles is provided.