Aqueous CO2-containing environment is ubiquitous in oil and gas production. Carbonate scales (e.g., calcite) tend to form in such an environment. Meanwhile, the CO2 corrosion of mild steel infrastructure may result in corrosion-induced scales including siderite (FeCO3). Previously, siderite was generally treated as a corrosion problem rather than a scale problem. However, the relationship between the corrosion-induced scale and other metal carbonate scales on the steel surface is unclear. For example, how does siderite influence calcite deposition on the mild steel? In this study, the mild steel corrosion and mineral carbonate scaling behaviors were investigated simultaneously in the presence of various cations such as Ca2+ and Mg2+. We observed a two-layer scale structure on the mild steel surface under simulated oilfield conditions. The inner layer is an iron-containing carbonate scale such as ankerite or siderite, while the outer layer is calcite. In addition, calcite deposition at a very low saturation index was observed when the inner layer was present. Furthermore, a common scale inhibitor [diethylenetriaminepentakis(methylenephosphonic acid) or DTPMP] can effectively mitigate calcite, siderite, and ankerite formation on the steel surface, but meanwhile, aggravate the steel corrosion because of the absence of protective scale layers.