A first study demonstrating the electrochemical cyclability of the LiAl alloy anode in the Li/polymer cells reported was carried out using LiAl/PEO30-LiN(CF3SO2)2/V2O5 cells in which the cell capacities were limited by LiAl anode. The cells fabricated with LiAl anode exhibited excellent electrochemical performance. The coulombic efficiency throughout the cell cycling was also close to 100% indicating that the lithium dendrite formation in LiAl/PEO30-LiN(CF3SO2)2/V2O5 cells is significantly reduced. The reduction in the lithium dendrite formation was attributed to lower lithium activity in the LiAl alloy and its higher open-circuit voltage (370mV versus Li). The cell voltage was, however, somewhat lower due to the higher open-circuit voltage of LiAl anode. The use of the LiAl alloy allows us to operate the cell at higher temperatures. Higher operating temperature improves the reaction kinetics while reducing the polarization losses associated with ohmic, mass transport, and diffusion.