The hitherto elusive phosphino formic acid molecule (H2PCOOH) was detected for the first time in the gas phase. Theoretical calculations revealed an unexpected kinetic stability of H2PCOOH compared to the isovalent carbamic acid (H2NCOOH) although the replacement of a single nitrogen atom by phosphorus decreases the bond order from a partial double (-C[double bond, length as m-dash]N-) to a single (-C-P-) bond. This work provides a fundamental framework to explore the synthesis and stability of derivatives of carbonic acid (H2CO3), in which one or both hydroxyl groups (OH) are replaced by hydride moieties involving third row atoms.