New synthetic routes to trifluoromethylated N-heterocycles based on condensations of 2-methoxy-2-methyl-5-(trifluoromethyl)furan-3(2H)-one with bifunctional N-nucleophiles are described. For the first time, trifluoromethyl-containing pyrazoles, pyrazolines and isoxazolines bearing hydrazone or oxime groups could be obtained by a one-pot strategy based on reactions of 5-(trifluoromethyl)furan-3(2H)-one with two equivalents of the corresponding hydrazines or hydroxylamine in the presence of an acid. The interaction of furan-3(2H)-one with ureas proceeded under mild conditions to furnish 1H-furo[2,3-d]imidazol-2(3H)-one derivatives in good yield. Further, a trifluoromethyl-containing quinoxaline derivative was obtained by condensation of furan-3(2H)-one with ortho-phenylenediamine