We have demonstrated highly selective and sensitive detection of Pb(II) and Cd(II) using a highly selective adsorptive porous magnesium oxide (MgO) nanoflowers. The MgO nanoflower-modified glassy carbon electrode was electrochemically characterized using cyclic voltammetry; and the anodic stripping voltammetric performance of bound Pb(II) and Cd(II) was evaluated using square wave anodic stripping voltammetry (SWASV) analysis. The MgO nanoflower-modified electrode exhibited excellent sensing performance toward Pb(II) and Cd(II) that was never observed previously at bismuth (Bi)-based electrodes. Simultaneous additions of Pb(II) and Cd(II) were investigated in the linear range from 3.3 to 22 nM for Pb(II) and 40 to 140 nM for Cd(II), and detection limits of 2.1 pM and 81 pM were obtained, respectively. Some foreign ions, such as Cu(II), Zn(II) and Cr(III) do not interfere with the detection of Pb(II) and Cd(II). To the best of our knowledge, this is the first example of a highly adsorptive metal oxide with hierarchical micro/nanostructure that allows the detection of both Pb(II) and Cd(II) ions.