The carbamoyloxime mechanophores were prepared following an adapted protocol established by us before and the synthesis is detailed in the Supplemental Information (Figure ). Briefly, a carbamoylimidazolinium salt was reacted with the corresponding oximes to obtain the diol precursors of the aldoxime (AO, R = H), the methylketoxime (MKO, R = Me), and the t-butylketoxime (TKO, R = tBu). Importantly, all carbamoyloximes showed well-distinguishable 1 H NMR spectra (Figure , S22, and S36) facilitating the observation of their reaction conversions. Subsequently, the diols were incorporated into the center of linear poly(methyl acrylate) (PMA) chains by esterification to the bifunctional initiator and subsequent telechelic Cu 0 -mediated controlled radical polymerization yielding the corresponding polymers PAO, PMKO, and PTKO each in five different molar masses Mn (Table ).