Research on hydrogen-bonded organic frameworks (HOFs) has been developed for quite a long time; however, those with both established permanent porosities and functional properties are extremely rare due to weak hydrogen-bonding interactions among molecular organic linkers, which are much more fragile and difficult to stabilize. Herein, through judiciously combining the superiority of both the moderately stable coordination bonds in metal organic frameworks and hydrogen bonds, we have realized a microporous hydrogen-bonded metal-complex or metallotecton framework HOF-21, which not only shows permanent porosity, but also exhibits highly selective separation performance of C2H2/C2H4 at room temperature. The outstanding separation performance can be ascribed to sieving effect confined by the fine-tuning pores and the superimposed hydrogen-bonding interaction between C2H2 and SiF62- on both ends as validated by both modeling and neutron powder diffraction experiments. More importantly, the collapsed HOF-21 can be restored by simply immersing it into water or salt solution. To the best of our knowledge, such extraordinary water stability and restorability of HOF-21 were observed for the first time in HOFs, underlying the bright perspective of such new HOF materials for their industrial usage.