We miniaturize geoelectrical acquisition using advanced microfabrication technologies to investigate coupled processes in the critical zone. We focus on the development of the complex electrical conductivity acquisition with the spectral induced polarization (SIP) method on a microfluidic chip equipped with electrodes. SIP is an innovative detection method that has the potential to monitor biogeochemical processes. However, due to the lack of microscale visualization of the processes, the interpretation of the SIP response remains under debate. This approach at the micrometer scale allows working in well-controlled conditions, with real-time monitoring by high-speed and high-resolution microscopy. It enables direct observation of microscopic reactive transport processes in the critical zone. We monitor the dissolution of pure calcite, a common geochemical reaction studied as an analog of the water–mineral interactions. We highlight the strong correlation between SIP response and dissolution through image processing. These results demonstrate that the proposed technological advancement will provide a further understanding of the critical zone processes through SIP observation.