Design and synthesis of degradable polymers is a burgeoning area of research to combat plastic waste buildup. Here, a cobalt-catalysed atom transfer radical polymerisation (ATRP) turned on by photothermal conversion is used to synthesize photodegradable non-alternating acrylate-isocyanide copolymers. A simple one-step protocol enables control over copolymerisation with good chain-end fidelity under mild conditions. Although fundamentally a ground state reaction, we demonstrate temporal control via a unique localized heating strategy. Lastly, we demonstrate the advantage of this polymerisation compared to more traditional ATRP protocols.