Charities have complained that CRB checks, necessary for volunteers working with children or other vulnerable groups, can take months to complete in some parts of the country.
The Home Office hopes that the trials, taking place nationwide and involving approximately 200 volunteers, will demonstrate how ID cards could shorten the process to a day or two.
But NO2ID, the pressure group campaigning against ID cards, branded the trials a sham and accused the Government of "using the sector for its own spin".
The trials have involved dummy ID cards and were designed to test the procedures that volunteers might go through.
Pretending they had been offered jobs at schools, volunteers filled in online forms. As part of the process, they had to submit photographs of themselves. According to a Home Office spokesman, the forms allowed mistakes to be picked up more quickly than would normally be the case.
A spokesman for the Scout Association said: "When an individual has moved around a lot, CRB checks can take as long as two or three months.
"So we are supportive of anything that speeds up the process of getting volunteers into organisations. We don't know whether ID cards will achieve this, but that's why we offered to do the trial."
Phil Booth, national coordinator of NO2ID, said: "The trials are based on the assumption that the national database would work correctly, but the Government has so far failed to demonstrate that. I'm deeply concerned that the voluntary sector doesn't get suckered by the latest Home Office spin."