Sugars and sugar-related molecules are ubiquitous in carbonaceous meteorites and in star-forming regions, but the underlying mechanisms of their formation have remained largely elusive. Herein, we report an unconventional synthesis of the hemiacetal, (R/S)-1-methoxyethanol (CH3OCH(OH)CH3), through quantum tunneling mediated reactions in low-temperature interstellar model ices composed of acetaldehyde (CH3CHO) and methanol (CH3OH). The detection of racemic 1-methoxyethanol through a bottom-up synthesis from simple, abundant precursor molecules within interstellar ices represents a vital starting point to the formation of complex interstellar hemiacetals. Once synthesized, hemiacetals may act as possible precursors to interstellar sugars and sugar-related molecules in deep space.