According to the European Standards (EN 450-1, EN 206), it is not permissible to use calcareous fly ash as an additive to concrete. However, other standards (for example, the American and Canadian ones) allow the use of high-calcium fly ash (type C) in concrete. As a result of brown coal combustion, a large amount of this type of fly ash is produced, and considerations on their use in concrete are in progress. Research into the influence of high-calcium fly ash on concrete durability is fundamental for dealing with that issue. The aim of the present research was to develop a new model of carbonation over time, also including calcareous fly ash content in the binder. The self-terminating model of carbonation is new, and not developed by other authors. In the current research, the former simplest model (a function of w/c ratio and time) is expanded with the calcareous fly ash to cement ratio. The basis is a statistically planned experiment with a large scope of two material variables (w/c ratio and fly ash to cement ratio). The main measured property is the carbonation depth after exposure to 4% of CO2 concentration (according to CEN/TS 12390-12). The model of carbonation obtained from this experiment is an output of the paper. Also, the idea of developing similar models for concrete families as a tool for designing concrete cover thickness for reinforced elements is described in the paper.