Limestone dissolution by -rich brine induces critical changes of the pore network geometrical parameters such as the pore size distribution, the connectivity, and the tortuosity which govern the macroscopic transport properties (permeability and dispersivity) that are required to parameterize the models, simulating the injection and the fate of . A set of four reactive core-flood experiments reproducing underground conditions ( and MPa) has been conducted for different partial pressures in order to study the different dissolution regimes. X-ray microtomographic images have been used to characterize the changes in the structural properties from pore scale to Darcy scale, while time-resolved pressure loss and chemical fluxes enabled the determination of the sample-scale change in porosity and permeability. The results show the growth of localized dissolution features associated with high permeability increase for the highest , whereas dissolution tends to be more homogeneously distributed for lower values of . For the latter, the higher the , the more the dissolution patterns display ramified structures and permeability increase. For the lowest value of , the preferential dissolution of the calcite cement associated with the low dissolution kinetics triggers the transport that may locally accumulate and form a microporous material that alters permeability and produces an anti-correlated porosity-permeability relationship. The combined analysis of the pore network geometry and the macroscopic measurements shows that regulates the tortuosity change during dissolution. Conversely, the increase of the exponent value of the observed power law permeability-porosity trend while increases, which appears to be strongly linked to the increase of the effective hydraulic diameter, depends on the initial rock structure.