Jones will have the experienced duo of hooker Amy Cokayne and number eight Alex Matthews as her vice captains.
England begin their defence of their Women’s Six Nations title against Ireland on 11 April.
Jones was born and raised in Cardiff, but moved across the border to England as a teenager and qualifies for the Red Roses through her English mother.
She made her England debut as an 18-year-old fly-half in a 26-7 defeat by New Zealand in July 2015. She has also starred in Sevens, travelling to the 2016 Olympics in Rio de Janeiro with Great Britain and then playing at Paris 2024.
When her Sevens contract was scrapped in 2020 as part of Covid cost-cutting measures, Jones worked as a delivery driver to make ends meet. Both Jones’ parents died within four months of each other in 2024 and she has spoken about playing through grief.
She started 12 of England’s 13 matches last year, only sitting out the 38-5 win over Italy in March.
“Meg reflects our values,” said Mitchell.
“Her personality, capabilities and leadership are hugely valuable to the Red Roses squad.
“She brings an infectious energy that lifts those around her and has had a huge influence on our culture and connections over the past three years.
“Not only is Meg highly respected, but she also consistently produces high-level performances and leads by example every time she takes to the field.”
England have won the past seven Women’s Six Nations and are on a run of 33 successive wins – stretching back to defeat in the Rugby World Cup final of 2022.