Numerical programs for simulating flow and reactive transport in porous media are essential tools for predicting reservoir properties changes triggered by CO2 underground injection. At reservoir scale, meshed models in which equations are solved assuming that constant macroscopic properties can be defined in each cells, are widely used. However, the parameterization of the dissolution–precipitation problem and of the feedback effects of these processes on the flow field is still challenging. The problem arises from the mismatch between the scales at which averaged parameters are defined in the meshed model and the scale at which chemical reactions occur and modify the pore network geometry. In this paper we investigate the links between the dissolution mechanisms that control the porosity changes and the related changes of the reactive surface area and of the permeability. First, the reactive surface area is computed from X-ray microtomography data obtained before and after a set of dissolution experiments of pure calcite rock samples using distinctly different brine–CO2 mixtures characterizing homogeneous to heterogeneous dissolution regimes. The results are used to validate the power law empirical model relating the reactive surface area to porosity proposed by Luquot and Gouze (2009). Second, we investigate the spatial distribution of the effective hydraulic radius and of the tortuosity, two structural parameters that control permeability, in order to explain the different porosity–permeability relationships observed for heterogeneous and homogeneous dissolution regimes. It is shown that the increase of permeability is due to the decrease of the tortuosity for homogeneous dissolution, whereas it is due to the combination of tortuosity decrease and hydraulic radius increase for heterogeneous dissolution. For the intermediate dissolution regime, identified to be the optimal regime for increasing permeability with small changes in porosity, the increase of permeability results from a large increase in the mean effective hydraulic radius of the sample.