We employed machine learning-augmented density functional theory (DFT) thermodynamic calculations to assess the stability of different AgOx structures under catalytic ethylene epoxidation reaction conditions. We found that there are multiple AgOx surface motifs that could co-exist under the relevant conditions. These included Ag surface oxides (e.g., AgO_p(4 × 4) and Ag1.83O) and atomic oxygen-covered Ag(111) surfaces. Furthermore, we employed DFT calculations to evaluate the energetics of different reaction mechanisms by which ethylene and oxygen can react on these surfaces. These studies revealed several energetically viable reaction pathways for ethylene epoxidation. Microkinetic modeling analyses, based on the DFT-calculated reaction pathways, showed that ethylene epoxidation can proceed on all surfaces and that multiple pathways, including those involving Langmuir–Hinshelwood and Eley–Rideal mechanisms, could be involved in selective and unselective reactions. The diversity of mechanisms that we discovered in the context of the relatively simple ethylene epoxidation reaction on Ag suggests that the richness and complexity of surface chemistry are most likely a rule rather than an exception in heterogeneous catalytic chemical transformations on metal surfaces and that the concept of a single or even a dominant mechanism and reaction intermediates might need to be revisited for many reactions.