Online electrochemical mass spectrometry (OEMS) is a promising analytical technique to monitor minor side reactions with gaseous species, taking place while charging and discharging a lithium-ion cell. However, besides the manifold examples of these custom-made systems and their application, a clear analytical view on the origin of the evolving gasses and their manifold interactions within the cell environment is missing and therefore given in this work. To get a better understanding of the complexity of gas evolution associated with electrochemical reactions in lithium-ion cells, the use of chronoamperometry as an analytical method was chosen. This led to a precise variation of the applied voltage and voltage-pulse length and enabled therewith a clear starting point of the electrochemically triggered reactions. It was found that chronoamperometry can be used to precisely trigger those reactions with gaseous products. Additionally, it was found that the release of gaseous species depends on many parameters including the cell configuration, the current, and the gas species. The response time determination showed that a custom-made highly porous electrode configuration had an overall better response behavior within minutes with differences for the respective gasses of interest, compared to a standard foil configuration cells. The herein presented methodology shows how an electroanalytical approach can help gain further insight into advanced hyphenated methods, such as OEMS in the context of studies of lithium-ion cells.