New reaction conditions were developed for the synthesis of E,Z-dienes from α,β-unsaturated aldehydes and heteroarylsulfones using the Julia reaction. In most cases under optimal conditions, the selectivity of the olefination reaction is better than 88:12 when a pyridylsulfone was used as the precursor. In addition, novel reaction conditions for the chemoselective oxidation of heteroarylthioethers that are compatible with alkenes and dienes are also reported.