More than 120 people attended two information sessions yesterday in Dunedin.
The first refugees, a group of about 45 Syrians, will arrive in Dunedin in April.
Working in teams of up to five, volunteers will be assigned to individual families for six months.
About 40 volunteers were needed for the first group and with refugees arriving regularly after that point, there would be opportunities for others.
Volunteers attend mandatory training before they can be assigned.
The volunteers are closely involved, especially in the first weeks.
They collect the families from the airport on their first day, having helped prepare their new home.
National programmes development manager Rachel O'Connor, of Wellington, said she was pleased to see so many Dunedin people wanted to help.
As Dunedin had been selected by the Government as a new resettlement centre, the meetings were historic, she said.
Everyday tasks, such as reading letters, visiting the supermarket, enrolling in school and seeking work could be daunting for refugees.
One volunteer had told Red Cross about a family who had placed plates and cups in the washing machine, Miss O'Connor said, to underline the fact that every volunteer's experience was unique, and families had different needs.
The "crazy multicultural misunderstandings'' that occurred between volunteers and refugees were "part of the fun''.
"You get to have a laugh and through that you build relationships.''
It was a big commitment for volunteers, who needed to be reliable and able to work with the other members of their team.
Red Cross communications manager Hanna Butler, of Wellington, who is also a volunteer, said she now sees her Colombian refugee family occasionally, but they had a strong bond.
She said the language barrier made for some difficulties at first, which was partly overcome by the useful, although not infallible, Google Translate.
Client services national lead Rachel Kidd, of Wellington, told the volunteers they would have close support from Red Cross staff.
The experience could be an eye-opener for "middle class'' people, as the refugees would initially be living on a benefit, which was not a lot of money.
Experience in dealing with Work and Income would be an advantage for volunteers, she said.
Before arriving, the refugees will spend six weeks at the Mangere Refugee Resettlement Centre.
