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Changes in pore (throat) size, surface roughness and mineralogy induced by supercritical‐CO₂‐water‐rock reactions impact petrophysical properties such as porosity, permeability, and especially wettability. Herein, we show that these changes directly impact relative permeability and capillary pressure curves, a fact rarely studied in the literature. In this work, we show that CO₂ contact angle changes emerge after Madison Limestone samples were soaked for 400 hours in CO₂‐enriched brine. Coreflooding results show that the water production rate and cumulative water production increased after the rock was exposed to carbonic acid. Moreover, the mercury capillary pressure decreased in meso‐ and macro‐pores, indicating the increase of size in these pores due to reactions. This compounded wettability and pore network alteration can directly affect CO₂ injectivity, migration and storage capacity. This fundamental insight into CO₂ geological storage processes should aid practitioners to reduce uncertainties in forecasting CO₂ distribution via injection simulation.