The agreement with Amicus, which is the first to be struck between the union and a print group, will give Polestar workers better access to their union learning representative (ULR).
Bernard Rutter, Amicus GPMS head of organising, learning and skills, said the agreement "will give workers in the Polestar group more access to their ULR and create more training and learning opportunities".
ULRs are union members whose job it is to improve skill levels through work with employers to make sure that all workers have access to training. They were given legal standing in April 2003.
The deal follows Polestar's roll-out last week of its PrintDynamics teaching software to secondary schools.
The package, developed in partnership with the Sector Skills Council for Science, Engineering and Manufacturing Technologies (SEMTA), will be sent to 10,000 schools over the coming six months.
Pupils from the Sir Henry Cooper School in Hull, who had beta-tested the software, travelled to London for the launch.
Polestar chief executive Barry Hibbert said: "Our objective is to help young people learn in the context of real jobs, and we hope PrintDynamics will open up the industry for all."
SEMTA chairman Lord Trefgarne added: "PrintDynamics shows an exciting world, and answers many questions young people have about printed products."
PrintDynamics will also be distributed with The Times 100 careers guide, which is sent to all secondary schools, and will also be sent out as part of the PrintIT! teaching pack.
Story by Josh Brooks
Have your say in the Printweek Poll
Related stories
Latest comments
"Sad to see another print company facing financial trouble. The industry is tough, and this highlights the ongoing challenges many are facing. Hope employees and customers get clarity soon."
"Not surprised, businesses need to prepare for these attacks rather than thinking that they're going to avoid them. At the very least, data needs to be fully protected with air gaps in place..."
"So much for growth then!"
Up next...

Six months after Charlesworth deal
TJ Books looks to appoint admins

Current timeframes are insufficient
Election print and postal pressures highlighted in AEA report

"Significant milestone"
Riso celebrates 20 years of inkjet

Strengthens existing product portfolio