Department for Education adviser Ndidi Okezie will join the leading youth work charity in January 2020, when Smee leaves to run the Youth Futures Foundation.
Former teacher Okezie's previous roles include six years on the executive board of Teach First, where she oversaw initiatives including for youth access and community action.
She currently sits on the DfE's character education advisory group, is vice president of the secondary school portfolio for education and publishing company Pearson, and is also a board member for youth homelessness charity Centrepoint UK, the National Citizen Service and The Mulberry Schools Trust.
Chair of UK Youth Lady Anne Stoneham, said: "Ndidi is a remarkable leader with decades of experience in supporting young people.
"Not only did she excite the board members on the panel, but she also impressed the UK Youth Voice panellists with her vision and understanding of how to grow UK Youth's impact, making it the best support to young people and youth workers.
We're excited to announce @Ndidi1st as the new CEO of UK Youth! Ndidi is deeply committed to youth work & youth equality and we can't wait to work together to ensure our ambitious future goes from strength to strength! Find out more here ?? https://t.co/N2MX4xBEr4 pic.twitter.com/QLpcmrGZDf
— UK Youth (@UKYouth) October 30, 2019
"On behalf of the whole board and staff team, we are thrilled to be welcoming her to the UK Youth family.
"She joins at an exciting time as the charity looks to launch its new strategy in 2020."
Okezie said her experience in youth volunteering since her teenage years has enshrined in her the value of the sector.
"I know how invaluable the support UK Youth provides to youth workers and young people is and so I'm looking forward to progressing the incredible legacy the team has built to date." she added.
"I'm passionate about social justice, quality access for underserved communities and the amplification of youth voice.
"I want to be of service; galvanising the UK Youth movement, championing our young people and removing barriers to ensure they have a valued seat at the table.
"I feel fortunate to be joining the charity at a time when its reputation and influence is stronger than ever.
"I hope to build on the achievements Anna and the team have delivered and I look forward to working together to ensure UK Youth's ambitious future goes from strength to strength."
Smee will leave on 7 November and her deputy Maddie Dinwoodie will be interim chief until 6 January 2020 when Okezie joins.
In 2017, Smee oversaw the merger of UK Youth and Ambition, and has been credited with increasing the charity's reputation and financial stability since joining in 2014.
The charity has been among the organisations calling for the government to develop a youth charter, which was announced earlier this year.
