This study investigated the feasibility of Raman microscopy for monitoring early surface carbonation of hardened cement pastes in real time for up to 7 days. Samples were exposed to natural carbonation (440 ppm CO2) and accelerated carbonation (4% CO2), and the evolution of calcium carbonate (CaCO3) polymorphs, portlandite, ettringite, C-S-H gel and unreacted cement particles was followed. Results showed that calcite is the main polymorph formed under both natural and accelerated carbonation. Under accelerated carbonation, the formation of calcite on the sample surface completed within 1 day whereas under natural carbonation, the formation of calcite is expected to continue beyond 7 days. The contents of portlandite and ettringite decreased rapidly under accelerated carbonation but much more gradually under natural carbonation. However, calcium silicate minerals in unreacted cement particles remained unchanged throughout the carbonation processes. Overall, this study demonstrated that Raman microscopy is a valuable tool for non-destructive real-time imaging of surface carbonation in cement-based materials.