The 21 pence rise for adults will be accompanied by a pay increase for 18-21 year-olds to £4.77 from £4.60 and a rise from £3.40 to £3.53 for 16 and 17-year-olds.
Employers who do not pass the pay-rise onto their employees face an unlimited fine and the risk of being tried in a crown court.
Business secretary John Hutton said the minimum wage "makes a real difference to the lives of many of our lowest-paid workers and protects them from exploitation. It also creates a level playing field for business and boosts the economy.”
Since it was introduced in 1999, the national minimum wage has risen 59 per cent.
The latest increase of 3.8 per cent, 1.6 per cent higher than the rate of inflation, has been criticised by the Association of Convenience Stores.
ACS Chief executive James Lowman said it was unfair that small businesses were expected to increase staff pay above the rate of inflation when the government was not doing the same for public sector workers.
“To expect businesses to deal with these above inflation increases year on year is unacceptable. We support the principle of a minimum level below which wages should not fall, but the continual increases of this level are not sustainable or fair to businesses."