A synthetic approach to stable enols was introduced and series of acyclic aliphatic solid enols were obtained and characterized. Relationship between the structure and the stability of these enols was discussed. Gaussian 09 calculations had been carried out to rationalize the stability of the enols. These enol structures were confirmed by (1)H NMR, (13)C NMR, MS, IR, partly by single crystal X-ray structure analysis and the protons exchange experiments. This work showed that very stable acyclic aliphatic enols can be synthesized efficiently without any purification.