A simple method for preparation of fluoroalkyl beta-enaminophosphonates 1 from alkylphosphonates 2 and perfluoroalkyl nitriles 3 is reported. Olefination reaction of functionalized phosphates 1 with aldehydes gives alpha,beta-unsaturated imines 5. Acid hydrolysis of these fluoroalkyl derivatives 5 affords alpha,beta-unsaturated ketones 6, while their selective reduction with hydrides leads to the formation of allylamines 7, enamines 8, and saturated ketones 9 or amines 10. Selective oxidative cleavage of the carbon-carbon double bond of allylamines 7 gives fluorinated alpha-amino aldehydes 12, alpha-amino ketones 13, or alpha-amino acid derivatives 14.