In an attempt to introduce monomer sequence control in a growing polynorbornene via ring-opening metathesis polymerization, we employ dioxepins to efficiently determine the location of the monomers on the macromolecule backbone. Owing to the acid-labile acetal group, dioxepins allow scission of the polymer at the point of the dioxepin insertion and thus provide an indirect way to determine the monomer location. Additionally, dioxepins are used as spacers in the synthesis of multiblock polynorbornenes that are readily cleavable to afford the individual polynorbornene blocks. (C) 2015 Wiley Periodicals, Inc.