Great changes occurred in the physical and chemical properties of the atmosphere in the North China Plain (NCP) in summer caused by PM2.5 dropping from 58 μg/m3 in 2015 to 36.0 μg/m3 in 2019. In this study, we first applied the WRF-Chem model to quantify the impact of PM2.5 reduction on shortwave radiation reaching the ground (SWDOWN), planetary boundary layer height (PBLH), and the surface concentration of air pollutants (represented by CO). Simulation results obtained an increase of 15.0% in daytime SWDOWN and 9.9% in daytime PBLH, and a decrease of −5.0% in daytime CO concentration. These changes were induced by the varied PM2.5 levels. Moreover, the variation in SWDOWN further led to a rise in the NO2 photolysis rate (JNO2) over this region, by 1.82 × 10−4~1.91 × 10−4 s−1 per year. Afterwards, we employed MCM chemical box model to explore how the JNO2 increase and the precursor decrease (CO, VOCs, and NOx) influenced O3 and HOx radicals. The results revealed that the photolysis rate (J) increase would individually cause a change on daytime surface O3, OH, and HO2 radicals by +9.0%, +18.9%, and +23.7%; the corresponding change induced by the precursor decrease was −2.5%, +1.9%, and −2.3%. At the same time, the integrated impacts of the change in J and precursors cause an increase of +6.3%, +21.1%, and +20.9% for daytime surface O3, OH, and HO2. Generally, the atmospheric oxidation capacity significantly enhanced during summer in NCP due to the PM2.5 dropping in recent years. This research can help understand atmosphere changes caused by PM2.5 reduction comprehensively.