The main aim of this work is to establish a sensor MESH network using an ESP-MESH networking protocol with the ESP32 MCU (a Wi-Fi-enabled microcontroller) for indoor and outdoor air quality monitoring in real time. Each sensor node is deployed at a different location on the college campus and includes sensor arrays (CO2, CO, and air quality) interfaced with the ESP32. The ESP-MESH networking protocol is a low-cost, easy-to-implement, medium-range, and low-power option. ESP32 microcontrollers are inexpensive and are used to establish the ESP-MESH network that allows numerous sensor nodes spread over a large physical area to be interconnected under the same wireless network to monitor air quality parameters accurately. The data of different air quality parameters (temperature, humidity, PM2.5, gas concentrations, etc.) is taken (every 2 min) from the indoor and outdoor nodes and continuously monitored for 72 min. A custom time-division multiple-access (TDMA) scheduling scheme for energy efficiency is applied to construct an appropriate transmission schedule that reduces the end-to-end transmission time from the sensor nodes to the router. The performance of the MESH network is estimated in terms of the package loss rate (PLR), package fault rate (PFR), and rate of packet delivery (RPD). The value of the RPD is more than 97%, and the value of the PMR and PER for each active node is less than 1.8%, which is under the limit. The results show that the ESP-MESH network protocol offers a considerably good quality of service, mainly for medium-area networks.