A novel biodegradable polymer-based nanocomposites with tunable multi-shape memory effect and temperature memory effect based on poly(propylene carbonate) (PPC)/graphene oxide (GO) was prepared. By using a solvent-exchange and solution co-precipitation approach, a high-content GO was incorporated into PPC matrix up to 20 wt% with excellent dispersion. The distributed architecture of GO could be tuned from a ‘GO dotted dispersion’ and ‘GO network’ to ‘GO compact layered structure’ with increasing GO content. GO sheets acted as cross-linking points, which confined the movement of PPC chains and increased the glass transition temperature (Tg) of PPC. The most eye-catching features were the appearance of two improved Tg with GO content over 10wt%, the one was corresponding to the slightly confined PPC, and the other could be attributed to the highly confined PPC. As a result, triple shape memory effect (TSME) was achieved via deformation at the two distinct Tg. In addition, experiments were designed to establish a temperature memory effect (TME) based on the stress free strain recovery, and it was found that the temperature corresponded to the maximum strain recovery rate could be quantitatively related to the deformation temperature. To the best of our knowledge, this is the first effort to take advantage of strong ‘nano-effect’ via formation of two separated Tg to access TSME and a broad Tg to access TME simultaneously. Our work suggests a controllable approach to design a tunable multi-shape memory and temperature memory polymer, which could expand to a broad range of polymer composites.