(1) Background: Children are the most vulnerable to pollution due to their decreased stature, heightened respiratory rate, and frequent outdoor engagement. PM2.5, nitrogen dioxide (NO2), ozone, and cold weather are associated with pediatric asthma. In this study, we investigated the nexus between air pollution, climate factors, and pediatric asthma emergency room visits (ERVs). (2) Method: Pediatric asthma ERV data for healthcare quality from the Taiwanese National Insurance in the Taipei area were obtained from 2015 to 2019. Air pollution and climate factor data were also collected. Poisson regression was employed to determine the relationships with relative risks (RRs). (3) Results: The incidence of pediatric asthma ERVs decreased, with a crude RR of 0.983 (95% CI: 0.98-0.986, p < 0.001). Fine particulate matter (PM2.5) had an adjusted RR of 1.102 (95% CI: 1.037-1.172, p = 0.002) and a 7.7 µg/m3 increase, and air temperature had an adjusted RR of 0.813 (95% CI: 0.745-0.887, p < 0.001) comparing between the highest and lowest quarter air temperature associated with pediatric asthma ERVs. (4) Conclusions: This inquiry underscores the positive associations of PM2.5 and cold weather with pediatric asthma ERVs. The findings could guide the government to establish policies to reduce air pollution and promote children's health.