The pore‐scale flow of CO2 and water in 2‐D heterogeneous porous micromodels over a Ca range of nearly three orders of magnitude was explored experimentally. The porous geometry is a close reprint of real sandstone, and the experiments were performed under reservoir‐relevant conditions (i.e., 8 MPa and 21 °C), thus ensuring relevance to practical CO2 operations. High‐speed fluorescent microscopy and image processing were employed to achieve temporally and spatially resolved data, providing a unique view of the dynamics underlying this multiphase flow scenario. Under conditions relevant to CO2 sequestration, final CO2 saturation was found to decrease and increase logarithmically with Ca within the capillary and viscous‐fingering regimes, respectively, with a minimum occurring during regime crossover. Specific interfacial length generally scales linearly with CO2 saturation, with higher slopes noted at high Ca due to stronger viscous and inertial forces, as supported by direct pore‐scale observations. Statistical analysis of the interfacial movements revealed that pore‐scale events are controlled by their intrinsic dynamics at low Ca, but overrun by the bulk flow at high Ca. During postfront flow, while permeability is typically correlated with total CO2 saturation in the porous domain (regardless of its mobility), the saturation of active CO2 pathways in the current study correlated very well with permeability. This alternate approach to characterize relative permeability could serve to mitigate hysteresis in relative permeability curves. Taken together, these results provide unique insights that address inconsistent observations in the literature and previously unanswered questions about the underlying flow dynamics of this important multiphase flow scenario.