We show that graphene supported on a hydrophobic and flat polymer surface results in flakes with extremely low doping and strain as assessed by their Raman spectroscopic characteristics. We exemplify this technique by micromechanical exfoliation of graphene on flat poly(methylmethacrylate) layers and demonstrate Raman peak intensity ratios I(2D)/I(G) approaching 10, similar to pristine freestanding graphene. We verify that these features are not an artifact of optical interference effects occurring at the substrate: they are similarly observed when varying the substrate thickness and are maintained when the environment of the graphene flake is completely changed, by encapsulating preselected flakes between hexagonal boron nitride layers. The exfoliation of clean, pristine graphene layers directly on flat polymer substrates enables high performance, supported, and non-encapsulated graphene devices for flexible and transparent optoelectronic studies. We additionally show that the access to a clean and supported graphene source leads to high-quality van der Waals heterostructures and devices with reproducible carrier mobilities exceeding 50 000 cm2 V−1 s−1 at room temperature.