Laser-ablated beryllium atoms have been reacted with methanol molecules during condensation in excess argon at 12 K. Absorptions due to CH3OBeH, CH3BeOH and CH3BeOBeH were observed and identified on the basis of isotopic IR studies with (CH3OH)-C-13, (CH3OH)-O-18, and CH3OD, as well as quantum chemical calculations. The beryllium atoms were observed to insert spontaneously into the O-H bond of methanol to form the CH3OBeH molecule, while the C-O bond insertion reaction to give the more stable CH3BeOH product requires activation energy. The CH3BeOH or CH3OBeH molecules could further react with a beryllium atom to form the CH3BeOBeH molecule.