Lead(II) oxides in bulk and thin film form were assessed as electrodes for lithium rechargeable batteries. Films were prepared by spray pyrolysis of aqueous solutions of Pb(CH3-COO)(2). 2H(2)O and deposited onto lead substrates at 175 degreesC. Films heated at 250 degreesC were found to consist of well-crystallized tetragonal PbO and evolve to the orthorhombic polymorph with prolonged heating. Cycling of the cells at a current density of 0.25 mA/cm(2) over the range 1.0-0.0 V led to the formation of various LiyPb alloys. Cells made from bulk oxides, whether tetragonal or orthorhombic, were found to exhibit poor performance (their capacity rapidly faded with cycling). By contrast, PbO him electrodes exhibited reversible capacity above 500 mA h/g beyond 40 cycles. The lead substrate must thus appreciably influence the electrochemical properties of the cell by facilitating adhesion of LiyPb microcrystals to its surface, thereby favoring alloying/de-alloying processes.