It hopes this will help to combat smuggling and tackle the chronic shortage of food and other basic items.
President Nicolas Maduro says gangs that operate in border areas will not have time to repatriate the money.
The 100-bolivar bill has lost most of its value over the past few years and is now worth about 2 cents (£0.015).
Venezuela, which is facing a serious economic and political crisis, has one of the world's highest inflation rates.
