Ministers have provided pound;14 million for projects to increase the numbers taking advantage of the trade union learning fund.
The fund, which has attracted pound;40m of investment since its 1998 launch, now runs 450 courses for workers signed up by shop-floor learning union reps.
Education Secretary Charles Clarke said: "Projects have been successful in reaching out to people who traditionally have been left out of learning opportunities, such as shift and part-time workers."
The fund has provided computers for online learning at a West Yorkshire biscuit factory, classrooms for Watford firefighters and computer courses for council workers in Blackburn.
More than 7,000 learning reps advise employees on training needs, liaise with training providers and negotiate time off for colleagues to study.
Since reps won new rights to carry out their duties, the number of people signing up for courses under the scheme has trebled to 25,000 a year.