PURPOSE: To easily obtain the subject compound useful as a raw material for 5-cyanopentanal, which is the precursor of -caprolactam, in a high yield by reacting 1-formyloxy or hydroxy-2-nitrosocyclohexane with an organic base and an alcohol or water.

CONSTITUTION: This method for producing 2-hydroxycyclohexane oxime comprises reacting (A) 1-formyloxy-2-nitrosocyclohexane or 1-hydroxy-2- nitrosocyclohexane with (B) an organic base such as a 3-13C aliphatic tertiary amine compound or a pyridine compound and (C) an alcohol or water e.g. in amounts of 1-10 equivalents and 1-300wt. times, respectively, based on the component A. The reaction is preferably performed in a reaction solvent such as acetonitrile at 70-100°C under the atmospheric pressure or an elevated pressure.