A green, rapid and continuous hydrothermal flow synthesis (CHFS) route has been employed to synthesise highly efficient and active novel heterogeneous catalysts. Tin doped zirconia (Zr-Sn-O) and tin doped zirconia/graphene nanocomposite (Zr-Sn/GO) have been assessed as suitable heterogeneous catalysts for the synthesis of dimethyl carbonate (DMC). The catalysts have been extensively characterized using powder X-ray diffraction (XRD), transmission electron microscopy (TEM), Brunauer-Emmett-Teller (BET) surface area measurement and X-ray photoelectron spectroscopy (XPS) analysis. Extensive batch studies for the synthesis of DMC via the transesterification of propylene carbonate (PC) and methanol (MeOH) using Zr-Sn/GO catalyst in a solvent free process were also conducted. The effect of various reaction conditions such as reactant molar ratio, catalyst loading, reaction temperature and reaction time has been extensively evaluated. Response surface methodology based on Box-Behneken Design (BBD) was employed to derive optimum conditions for maximising PC conversion and DMC yield. The correlations and interactions between various variables such as MeOH:PC ratio, catalyst loading, reaction temperature, reaction time and stirring speed were extensively studied. A quadratic model by multiple regression analysis for the PC conversion and DMC yield was developed and verified by several methods BBD revealed that optimum conditions for high yield values of DMC are 12.33:1 MeOH:PC molar ratio, 446.7 K, 4.08 h and 300 rpm using 2.9% (w/w) Zr-Sn/GO nanocomposite. The maximum predicted responses at the optimum conditions are 85.1% and 81% for PC conversion and yield of DMC respectively. Experimental results at optimum model predicted reaction conditions agree very well with the model predicted response, where 82.4% PC conversion and 78.2% yield of DMC were obtained. Catalyst reusability and stability studies have been conducted at optimum reaction condition to investigate the long term stability of Zr-Sn/GO and it has been found that the catalyst could be reused more than six times (about 42 h) without losing its catalytic activity. These experimental and model predicted values showed an excellent agreement for tin doped zirconia/graphene nanocomposite as a heterogeneous catalyst for the synthesis of DMC from PC and MeOH.