A novel one-pot approach for the synthesis of trichloroacetates is described. Use of inexpensive, commercially available trichloroacetonitrile as a trichloroacyl source has made this protocol have more industrial applications. This one-pot approach is applicable to a wide range of alcohols as demonstrated by 28 examples with good to excellent yields in the order of 93%. Trichloroacetates were characterized by infrared, NMR spectra and further the structure of 2-(1,3-dioxoisoindolin-2-yl)ethyl-2,2,2-trichloroacetate was confirmed by single-crystal X-ray diffraction. Moreover, benzyl trichloroacetates synthesized were converted into corresponding benzyl iodides in good yields (51-70%). In addition, bypassing harsh reagents, use of cheaper, commercially available sodium iodide as nucleophile and mild reaction conditions are some of practical features of this methodology.