We have successfully developed a strategy for the first time for the enantioselective Rh-TaniaPhos catalyzed asymmetric hydrogenation of unprotected β-enamine phosphonates to free β-amino phosphonates directly with good enantioselectivities (80%-86% ee) and high conversions (>99% conversion). The resulting chiral free β-amino phosphonates and their derivatives are important intermediates in biochemistry and pharmaceuticals.