Since the observation of the first sulfur-containing molecule, carbon monosulfide (CS), in the interstellar medium (ISM) half a century ago, sulfur-bearing species have attracted great attention from the astrochemistry, astrobiology, and planetary geology communities. Nevertheless, it is still not clear in which forms most of the sulfur resides in molecular clouds, an unsolved problem referred to as "sulfur depletion". Reported herein is the formation of thioformic acid (HCOSH)─the simplest thioacid─in interstellar ice analogues containing carbon monoxide (CO) and hydrogen sulfide (H2S) at 5 K. Utilizing single photoionization reflectron time-of-flight mass spectrometry and isotopically labeled molecules, thioformic acid molecules were selectively photoionized in the temperature-programmed desorption phase. These studies unravel a key reaction pathway to thioformic acid, an organic molecule recently detected toward the giant molecular cloud G+0.693-0.027 and the hot core G31.41+0.31, thus shedding light on interstellar sulfur chemistry.