A practical one-pot method for the synthesis of biimidazoline has been developed. A variety of biimidazolines were prepared smoothly under mild conditions and were evaluated in Pd-catalyzed asymmetric allylic alkylation of 1,3-diaryl-2-propenyl acetate with malonate. The catalytic system gave the desired adducts in good yield and with excellent enantioselectivities (up to 97% ee).