The preparation of 4-alkoxy-1,1,1-trichloro-3-alken-2-ones (enones), important synthetic tools for the heterocyclic synthesis, from cheap and easily accessible starting materials, is reported. The applications of the enones in the synthesis of isoxazoles, pyrazoles, pyrimidines and other heterocycles are also reported. This review was grouped into two main sections: (i) synthesis of 4-alkoxy-1,1,1-trichloro-3-alken-2-ones and derivatives and (ii) applications of 4-alkoxy-1,1,1-trichloro-3-alken-2-ones in heterocyclic synthesis.