We　herein　describe　a　general　approach　to　5-trifluoromethyl　1,2,4-triazoles　via　the　[3　+　2]-cycloaddition　of　nitrile　imines　generated　in　situ　from　hydrazonyl　chloride　with　CF3CN,　utilizing　2,2,2-trifluoroacetaldehyde　O-(aryl)oxime　as　the　precursor　of　trifluoroacetonitrile.　Various　functional　groups,　including　alkyl-substituted　hydrazonyl　chloride,　were　tolerated　during　cycloaddition.　Furthermore,　the　gram-scale　synthesis　and　common　downstream　transformations　proved　the　potential　synthetic　relevance　of　this　developed　methodology.