Enzymatic catalysis is largely based on cooperativity between a metal center and functional organic molecules located at its surrounding folds. Inspired by this biological concept, we are developing molecules that aim to mimic enzymatic cooperativity. Thus, we design intramolecular catalytic systems in which both the catalytic group(s) and the non-reacting components are tethered in close proximity to each other, aiming to address current challenges in the catalytic activation of small molecules. One of our approaches is to incorporate several functional side chains within peptoids, N-substituted glycine oligomers, for mimicking a second coordination sphere about embedded metal centers. Peptoids can be efficiently generated by a solid-phase method that enables the inclusion of innumerable functional groups at specified N-positions along their spine. Thus, they can be used as a tool for studying the cooperativity between catalytic groups placed on one scaffold. In my talk I will show how we utilized this approach for the construction of Cu- and Co-peptoid complexes that catalyze electrochemical and photochemical water oxidation, with high turn-over-numbers via intramolecular cooperativity. [1-6] Specifically, I will demonstrate how the second coordination sphere about the metal center, created by the peptoid scaffold and non-catalytic side chains facilitate the reaction via stabilization of the catalytic metal center and by enabling proton shuttling.