Using first principles methods, we investigated the possibility of inducing d 0 magnetism in α-PbO. The Pb i interstitial defect was found to acquire magnetic properties after its incorporation into the α-PbO crystal structure. The Pb i interstitial defect generates a p localized state with two electrons on-site, the spin alignment of which is governed by Hund׳s rule, thereby leading to the formation of the local magnetic moment 2μB. The magnetic coupling between defects is a function of the occupancy of the defect states. For two defects in their zero charge state Pbi(0), the antiferromagnetic coupling is more stable. The Pb interstitial defects in the charge state Pbi(1+) already have the ferromagnetic ground state. The magnetic coupling was found to be driven by long-range order interactions. The critical limit on the defect concentration required to establish magnetic percolation above room temperature is about 10 20 cm −3 , which may be possible when Pb i defects are formed on the surface of a single crystal. The substitution of the Pb interstitial defect with the non-magnetic elements of the s2px outer shell (the local magnetic moment is defined by 1≤x≤3) was found to be a potential means for tuning the magnetic behavior.