The NA48/2 experiment at CERN reports the first observation of the K±→π±π0e+e− decay from an exposure of 1.7×1011 charged kaon decays recorded in 2003–2004. A sample of 4919 candidates with 4.9% background contamination allows the determination of the branching ratio in the full kinematic region, BR(K±→π±π0e+e−)=(4.24±0.14)×10−6. The study of the kinematic space shows evidence for a structure dependent contribution in agreement with predictions based on chiral perturbation theory. Several P- and CP-violating asymmetries are also evaluated.