The COVID-19 lockdown presented a peculiar opportunity to study a shift in the photochemical regime of ozone production in Quito (Ecuador) before and after mobility restrictions. Primary precursors such as NO and CO dropped dramatically as early as 13 March 2020, due to school closures, but ambient ozone did not change. In this work we use a chemical box model in order to estimate regimes of ozone production before and after the lockdown. We constrain the model with observations in Quito (ozone, NOx, CO, and meteorology) and with estimations of traffic-associated VOCs that are tightly linked to CO. To this end, we use the closest observational data of VOC/CO ratios at an urban area that shares with Quito conditions of high altitude and is located in the tropics, namely Mexico City. A shift in the chemical regime after mobility restrictions was evaluated in light of the magnitude of radical losses to nitric acid and to hydrogen peroxide. With reduced NOx in the morning rush hour (lockdown conditions), ozone production rates at 08:30–10:30 increased from 4.2–17 to 9.7–23 ppbv h−1, respectively. To test further the observed shift in chemical regime, ozone production was recalculated with post-lockdown NOx levels, but setting VOCs to pre-lockdown conditions. This change tripled ozone production rates in the mid-morning and stayed higher throughout the day. In light of these findings, practical scenarios that present the potential for ozone accumulation in the ambient air are discussed.