We have reported the first chiral spiro bis(isoxazoline) ligands (SPRIXs) bearing a chiral spiro skeleton and two isoxazoline rings, and demonstrated the first example for the use of isoxazoline in transition metal-catalyzed enantioselective reactions.  Employing combinatorial approach starting from diethyl malonate and alkenyl and/or alkynyl halides, syntheses of various spiro-type ligands which contain isoxazoline and/or isoxazole have been achieved.