N-(Diphenylmethylene)-2,2,2-trifluoroethanamine acts as a versatile fluorine-containing building block, and from which N-(α-fluorovinyl)azole derivatives were readily prepared in good yields with relatively high stereoselectivity by using various N–H containing heterocycles as nucleophiles via vinylic substitution reactions (S_NV) in the presence of LDA and K₃PO₄ in a one-pot process.