Since the outbreak of the COVID-19 pandemic in 2020, the habits of the population have changed significantly, leading to a rapid popularization of telematic activities, especially teleworking and e-learning. Telework can be a solution to weekday rush hour congestion as commuting is a major source of air pollutant emissions in urban areas, especially nitrogen oxides such as NO2. To test the possible effect of air quality improvement due to teleworking, the present work analyzes by weekday the concentration of pollutants between a pre-pandemic period in 2019, where teleworking was not as widespread, and the post-pandemic period in 2022, together with traffic levels for a central area of the city of Madrid. The results indicate a reduction in NO2 concentration and urban traffic recorded in 2022, which may be due to an increase in the number of people teleworking on a regular basis. By days of the week, it has been found that pollution peaks change between the two periods, occurring in 2022 on Tuesday and Fridays, and not on Mondays. The study may be inspiring and help decision makers to propose plans and strategies that include the proposal of which days of the week could be more beneficial to telework in order to improve the air quality of urban areas.