Summary: A soluble, regular, ethoxy‐capped, ladder poly(silsesquioxane) ( EtO‐LPOAS ) has been successfully synthesized by means of the concerted H‐bonding template of silanol and amido groups, through a new template monomer M : tetraethoxy disiloxane bisamide compound. EtO‐LPOAS was characterized by X‐ray diffraction (XRD), 29Si NMR spectroscopy and DSC measurements. The results confirm the presence of the regular, ladder structure of EtO‐LPOAS . This synthetic method has opened a new route to other new kinds of functional ladder poly(silsesquioxane)s.