Thiol-mediated uptake is receiving increasing attention as an innovative way to penetrate cells. Taking advantage of dynamic thiol-disulfide exchanges at the cell surface, both polymeric and small molecule transporters were introduced by our group, achieving excellent cellular uptake properties with minimal toxicity. Studying the dynamic covalent chemistry of such transporters, we could better understand their mode of action to try and improve their efficiency, and gain access to dynamic covalent oligomers in a controlled fashion.