New and efficient methods were developed to prepare ketene organyltelluroacetals in moderate to excellent yields. This was accomplished by reaction of phenyl-or butyltelluromethylphosphonates with phenyl-or butyltellurenyl halides and aldehydes or cyclohexanone, under basic conditions. This Horner–Wittig protocol allows the preparation of several new tri-and tetra-substituted olefins.