In this paper, an electrochemical sensor was developed for detecting heavy metal ions by using contains O, S and N atoms polymer hollow nanosphere materials for the electrochemical simultaneous detection of Pb2+ and Cu2+. poly(2,5-bis-(2,3-dihydrothieno[3,4-b][1,4]dioxyin-5-yl)pyridine) hollow nanosphere (poly(BPE)HNs) and poly(3,6-bis(3,4-ethylenedioxythienylpyridazine) hollow nanosphere (poly(EPE)HNs) were prepared by via chemical oxidative polymerization method. And the resulting products were characterized by FT-IR, UV-vis, TGA, XRD, TEM and SEM. The results indicated that two kinds of polymers were prepared successfully. Furthermore, the electrochemical sensors were applied for the electrochemical determination of Pb2+ and Cu2+ using DPV method. And the results indicated that poly(BPE)HNs modified glassy carbon electrode (poly(BPE) HNs/GCE) exhibited linear detection range from 0.012-4 mu M and 0.016-4 mu M for the Pb2+ and Cu2+, with the sensitivity of 19.51 mu A/mu M and 4.87 mu A/mu M. The detection limits (S/N = 3) of 0.005 mu M and 0.012 mu M, respectively. The real sample analysis suggested that the poly(BPE)HNs modified electrode can be applied for the detection of the Pb2+ and Cu2+ ions in tap water samples.