Herein we describe a self-acid-enabled chemo-, regio-, and stereospecific cis-hydrophenoxylation of ynamides under reagent-free conditions. The presence of a non-polar solvent such as toluene was found to be beneficial to facilitate the rate-limiting proton transfer between phenols and ynamides to form an intimate ion pair, which is followed by a swift nucleophilic attack of the phenolate oxygen on keteniminium, fulfilling the overall hydrofunctionalization event. This protocol is operationally simple and easily scalable, tolerates a wide variety of functional groups, and shows good compatibility with the requirements of modern green chemistry.