The list of 198 firms owed a total of £466,219 in arrears and included football clubs, recruitment firms, care homes and hairdressers.
Top of the list was a London restaurant which owed almost £100,000 to 30 employees.
The Department for Business, Energy and Industrial Strategy said all the money owed had been paid back to workers.
The list was the largest of its kind since the "naming and shaming" scheme was introduced in October 2013.
The department said 688 employers in total have been publicly identified for flouting the law, with total arrears of more than £3.5m.
Business Minister Margot James said: "It is not acceptable that some employers fail to pay at least the minimum wage their workers are entitled to.
"So we'll continue to crack down on those who ignore the law, including by naming and shaming them."
Restaurant San Lorenzo in Wimbledon, South West London, owed £99,541.98 to 30 workers, while Premier Recruitment Ltd in Derby owed £34,797.33 to 424 workers.
Also on the list were football clubs Blackpool FC and Brighton and Hove Albion, which owed £2,861.64 to one worker.
Brighton and Hove Albion said its reputation had been "unfairly tarnished" by its inclusion on the list, claiming the case was a "minor administrative error" which resulted from being "over generous" in paying expenses to someone on work experience two years ago.
A spokesman for the club insisted: "We are one of the few clubs who pays its staff over and above the National Living Wage."
TUC general secretary Frances O'Grady called for the "worst offenders" to be prosecuted, adding: "Bosses who try to duck the minimum wage must have nowhere to hide.
"The level of underpayment in some cases is truly eye-watering."
The list comes after the new National Living Wage was introduced in April, requiring employers to pay at least £7.20 an hour to employees aged 25 and over.
However, the Living Wage Foundation calculates that a rate of £8.25 per hour is required to meet the cost of living, rising to £9.40 in London. Some employers pay this higher living wage voluntarily.
The National Living Wage of £6.70 an hour applies to workers aged 21 to 24, with lower rates for younger people and apprentices.
The government's list includes firms that have failed to pay either the minimum wage or the National Living Wage.
Conor D'Arcy from think tank the Resolution Foundation backed the government's policy of naming and shaming but added: "With the number of people on the wage floor set to treble over the next four years, the government will need to strengthen its resources for enforcing both the national minimum wage and the national living wage."
Green Party peer Baroness Jones said: "The government must introduce a real Living Wage, calculated by the actual cost of living, as called for by the Living Wage Foundation and the Green Party, among others.
"This is the only way to ensure people can afford to live in Britain today."
The government has publicly named almost 200 companies who have failed to pay the minimum wage to employees.