A copper catalyzed annulation–aromatization of benzyl trifluoromethyl ketimines with 3-acryloyloxazolidin-2-ones for the synthesis of 3-fluoropyridines through double C–F bond cleavages has been developed. In this approach, the annulation occurred between the in situ formed dienes from trifluoromethyl ketimines via the first C-F bond cleavage and 3-acryloyloxazolidin-2-ones. Then the aromatization afforded 3-fluoropyridines in moderate yields through the second C–F bond cleavage. The 3-fluoropyridine products could be further hydrolyzed to multi-substituted 3-pyridinecarboxylic acids.