2,2,2-Trifluoroacetaldehyde O-(aryl)oxime was employed for the [3 + 2] cycloaddition of pyridinium 1,4-zwitterionic thiolates for the synthesis of 2-trifluoromethyl 4,5-disubstituted thiazoles. The reaction works well with various substituted pyridinium 1,4-zwitterionic thiolates in moderate to good yields. The synthetic potential of the obtained 2-trifluoromethyl 4,5-disubstituted thiazoles was demonstrated.