Iodosobenzene (PhIO) is a well‐known hypervalent iodine reagent for its Lewis acidic oxidizing capability. In recent times it has been repeatedly proven to be a powerful tool for the development of toxic, costly transition‐metal‐free advanced and impressive methodologies to construct diverse array of different heterocycles. In this review some selected viable and innovative strategies from 2007 to 2016 have been contemplated. Sometimes mechanistic proposals were also taken as prime consideration since synthetic organic chemists are providing fresh stimuli to reinforce the theoretical predictions to grasp the unique nature of PhIO in dissimilar conditions. Convenient and environmentally friendly cyclization and cycloaddition protocols were delineated adequately to integrate the practical findings and mechanistic points of view.