In recent decades there has been uprising interest in the medicinal properties of organoselenides. These ubiquitous structural have their wide applications in material sciences, in catalysis and modern organic transformations. Research studies have led to important discoveries regarding selective C–Se bond formation and in this context a notable approach is direct selenylation. In this regard, nitrogen- or oxygen-containing arenes with organoselenides have appeared as a very important class of molecules, with diverse applications in the biological sciences. Therefore, their synthesis via sustainable routes have attracted considerable attention. As part of our wider research program aimed at designing and developing eco-friendly processes, herein we report, urea-hydrogen peroxide (UHP)- mediated direct C(sp2)-H bond selenylation of imidazoheteroarenes and simple activated arenes. Under optimized reaction conditions, one equiv. of (hetero)arene, 0.55 equiv. of various diorganyl diselenides, 1.1 equiv. of UHP in ethyl lactate as solvent, resulted the desired selenylated products in good to excellent yields.