This chapter presents the synthesis, characterisation and degradation of amphiphilic polymer co-networks (APCNs) based on dimethacrylate-end-linked linear amphiphilic ABA triblock copolymers prepared using labile bifunctional initiators. Three co-network families are described, each synthesised using a different ‘living’/controlled polymerisation technique, group transfer polymerisation, atom transfer radical polymerisation and reversible addition-fragmentation chain transfer polymerisation and employing the appropriate labile bifunctional initiator. The kinetics of degradation, the nature of the degradation products and the evolution of the swelling degrees are reported. A small-angle neutron scattering study is also presented, revealing two (changing) correlation peaks: one due to the scattering centres within the degrading APCNs, and the other due to the scattering by the polymeric degradation products which are amphiphilic star block copolymers.