A homochiral microporous hydrogen-bonded organic framework (HOF-2) based on a BINOL derivative has been synthesized and structurally characterized to be a uninodal 6-connected {3(3)5(5)6(6)7} network. This new HOF exhibits not only a permanent porosity with the BET of 237.6 m(2) g(-1) but also, more importantly, a highly enantioselective separation of chiral secondary alcohols with ee value up to 92% for 1-phenylethanol.