Heterofunctionalization is an important tool for synthesis of bioactive molecules and to create new chemical entities. We developed a green and efficient method for the direct C-H/N-H cross dehydrogenative coupling of aryl naphthoquinone with imidazole in the absence of metal, ligand, and additive. Most interestingly, the synthesized imidazoloquinones were utilized as a key intermediate for unprecedented C-S, C-N, and highly valuable C-O bond heterofunctionalization. Important features of present findings, compared to previously known methods, are C-H and C-N bond activation under metal free condition, hetero functionalization of imidazoloquinone, no need for reoxidation, broad substrate scope, and high yields.