The overall objective of this research was to study children’s respiratory illness levels in Targoviste (Romania) in relationship to the outdoor concentrations of airborne particulate matter with an aerodynamic diameter below 2.5 µm (PM2.5). We monitored and analysed the PM2.5 concentrations according to a complex experimental protocol. The health trial was conducted over three months (October–December 2015) and required the active cooperation of the children’s parents to monitor carefully the respiratory symptoms of the child, i.e., coughing, rhinorrhoea, wheezing, and fever, as well as their outdoor program. We selected the most sensitive children (n = 25; age: 2–10 years) with perturbed respiratory health, i.e., wheezing, asthma, and associated symptoms. The estimated average PM2.5 doses were 0.8–14.5 µg·day−1 for weekdays, and 0.4–6.6 µg·day−1 for the weekend. The frequency and duration of the symptoms decreased with increasing age. The 4- to 5-year old children recorded the longest duration of symptoms, except for rhinorrhoea, which suggested that this age interval is the most vulnerable to exogenous trigger agents (p < 0.01) compared to the other age groups. PM2.5 air pollution was found to have a direct positive correlation with the number of wheezing episodes (r = 0.87; p < 0.01) in November 2015. Monitoring of wheezing occurrences in the absence of fever can provide a reliable assessment of the air pollution effect on the exacerbation of asthma and respiratory disorders in sensitive children.