The Unit, based in the Department for Education and Employment but working with other departments and agencies, will head the government's "crusade" to improve adult literacy and numeracy.
Ms Pember, awarded an OBE for 21 years of service to further education this year, begins her new role in November. She said her first priority would be a clear strategy to help the estimated seven million adults whose literacy levels are below 11-year-olds'.
She said the Basic Skills Agency was doing "a brilliant job" and the new unit would supplement their work.
"We want to make sure that participation is raised. To do that we have to find really exciting, powerful innovative ways to engage learners. We need to be creative."
She said television programmes could highlight basic skills issues and provide solutions - like the recent illiteracy storyline on Channel 4's Brookside.
She rged employers to "take responsibility" to ensure workforces had adequate basic skills.
The 47 local Learning and Skills Councils, which begin work next April, will each have a basic skills officer to act as the unit's "eyes and ears" on the ground.
Government funding for basic skills, enhanced by a further pound;20.25 million announced in the May budget, will total pound;280m this year - still significantly below the pound;600m needed according to the report of Sir Claus Moser.
But better allocation could release more money. The basic skills unit at Canterbury College had to bid for money from up to 15 different sources, she said. "What the government have made available ... is excellent. We have to make sure it is used to maximum advantage."
Welcoming her appointment, lifelong learning minister Malcolm Wicks said: "She has a crucial task in taking forward the Government's drive to tackle poor literacy and numeracy skills. We will make this issue - a sad legacy of decades of underachievement - a top priority."