Apple skin color is essential for market value. Therefore, this study evaluated the efficiency of pneumatic defoliation (PD) on the enhancement of red skin color and anthocyanin pigments in ‘Picnic’ apples. Three weeks before harvesting, apple trees were treated with PD with low- (0.7 bar) and high- (0.9 bar) air pressure at a tractor driving speed of 2 km/h. Undefoliated trees served as controls. Higher leaf defoliation and leaf damage rates were observed in the high-PD treatment than those in the low-PD treatment. Photosynthetically active radiation inside the canopies was the highest in trees subjected to high-pressure PD than in those that underwent low-pressure PD and the controls. At harvest, the fruit color (a*) value, red-colored area, and anthocyanin content in the fruit skin were the highest in the high-PD treatment, intermediate in the low-PD treatment, and the lowest in the control treatments. Additionally, a higher expression of anthocyanin biosynthetic genes was observed in both defoliation treatments, especially under high PD. However, except for higher flesh firmness under low PD, the L* and b* values and fruit quality indices (fruit weight, starch pattern index, titratable acidity, soluble solids content, and sunburn occurrence) were not significantly affected by either PD treatment. In conclusion, PD can be used to enhance skin coloration and anthocyanin pigments in apples; further PD with high air pressure achieved optimum red skin coloration in ‘Picnic’ apples.