The man gave the woman a US $500 bill - a denomination last printed in 1945 and only in very limited circulation.
Police in Malaysia were called after the housekeeper found the note was a fake when she tried to change it to local currency at a bureau de change.
When officers arrested the man they found fake currency with a face value of $66m in bundles of $1m, $100,000 and $500 notes in his Kuala Lumpar hotel room.
The man now faces up to 10 years jail if convicted of possessing counterfeit currency.
The largest denomination of US currency ever printed by the US Treasury Department was a special edition one for $100,000 in 1934.
The largest US note currently in wide circulation is a $100 bill.