Copolymers containing thioester and thioketal groups were obtained by copolymerization of five- to seven-membered ring thionolactones (TLs) with vinyl pivalate (VP). With the help of a degradation study on thioester and thioketal model compounds, we report the orthogonal reactivity of such incorporated links with thioesters being selectively cleaved by aminolysis and thioketals by peroxides. Orthogonal stepwise degradation of poly(TL-co-VP) copolymers was achieved using isopropylamine and benzoyl peroxide as shown by SEC. Bleach was identified as a universal agent for accelerated degradation. A good correlation between oligomer length after degradation and estimated polymer mass loss is also reported.