We detail a polymer synthetic methodology that merges the techniques of insertion and radical polymerization methods into a single organometallic catalyst. This metal-organic insertion / light initiated radical (MILRad) polymerization technique is successful at polymerizing methyl acrylate (MA) and hexene using light as a critical stimulus. In this study, we describe a novel approach that uses visible light (460 nm) to switch the catalytic activity of a cationic palladium catalyst from an insertion route to a radical process in a reversible manner, turning the catalyst into a photocatalytic system when desired. It was discovered that a selective polymerization of a mixture of MA and hexene is accomplished using light and dark cycles respectively. This polymerization process enables the copolymerization of MA and hexene to create homo- and block copoly-mer architectures facilitated solely by visible light. In this work, we show the synthesis of MA homopolymers in controlled molecular weight ranges (Mn 50-300 kDa) with low dispersities (~1.5) and the synthesis of MA (A) and hexene (B) block copolymers. Starting with a mixture of MA and hexene and switching between dark and light cycles afforded a series of AB, ABA, ABAB and BA, BAB, BABA block copolymers in a sequential and one-pot process with molecular weight ranges of (Mn 15-60 kDa) and well controlled polydispersity (~1.3-2.0). The use of a photocontrollable "switch" is a novel and facile ap-proach to gain access to a wide variety of polymers that were not accessible using a single organometallic catalyst.