This comprehensive review highlights the diverse chemistry and applications of polymer-supported triphenylphosphine (PS-TPP) in organic synthesis since its inception. Specifically, the review describes applications of the preceding reagent in functional group interconversions, heterocycle synthesis, metal complexes and their application in synthesis, and total synthesis of natural products. Many examples are provided from the literature to show the scope and selectivity (regio, stereo, and chemo) in these transformations.