The singly Cabibbo suppressed (SCS) decays D→πa0, with a0≡a0(980), have been measured with the branching-fraction ratios rex+/−≡B(D0→π−a0+)/B(D0→π+a0−)=7.5−0.8+2.5±1.7 and rex+/0≡B(D+→π0a0+)/B(D+→π+a00)=2.6±0.6±0.3, deviating significantly from the short-distance expectations (r+/−,r+/0)≃(0.07,0.2). This discrepancy indicates the necessity of long-distance rescattering effects. In particular, the process D→K∗K→a0π generates Ms comparable in magnitude to Md in the amplitude M=λdMd+λsMs, with λq≡Vcq∗Vuq, accompanied by nontrivial strong phases essential for CP violation. Consequently, the direct CP asymmetries naturally arise at the O(10−3) level, for example, ACP(D0→π−a0+)=(−0.7±0.1±0.1±0.1)×10−3, ACP(D+→π0a0+)=(−1.4±0.1±0.1±0.1)×10−3, and ACP(D0→π+a0−)=(−2.1±0.9±1.1±0.4)×10−3. These results establish SCS D→πa0 decays as a new avenue for probing CP violation.