The reaction of 2‐oxo‐2H‐chromene‐3‐carboxamide (1) with carbon disulfide afforded 1‐mercaptopyrrolo[3,4‐c]chromene ‐3,4‐dione (3). The latter compound was utilized as versatile building block for new azole systems via incorporating in a series of manipulations including cyclocondensation reactions. The structure of the newly synthesized compounds has been confirmed by IR, 1H NMR, 13C NMR, mass spectral, and elemental analysis. Furthermore, some selected compounds were screened in vitro for their antimicrobial activities. The results declared that most of the synthesized compounds have high antimicrobial activity.