Organoselenium chemistry has gained much interest of researchers due to its applicability in synthetic chemistry and catalysis and in biology, particularly after the discovery of selenocysteine amino acid in mammals. Consequently, novel organoseleniums with desired functions and newer synthetic methodologies are being discovered. The construction of carbon-chalcogen in these compounds has been achieved mainly by using transition metal-catalyzed methodology. However, a mild and cost-effective base/oxidant dependent oxidative approach provides an alternative approach to TM-catalyzed methodology. In this highlight review, newer methods mainly relying on the oxidative approach, which is sustainable and does not require pre-functionalized substrates to construct organoseleniums, have been discussed. The organoselenium compounds also serve as an effective catalyst for the transformation of several organic transformations with the aid of hydrogen peroxide/TBHP/halogens or halogenated organoseleniums to activate organoseleniums. Catalytic properties of organoselenium toward the activation of an abundant and greener oxidant such as oxygen is also highlighted.