On 6 August 2006, Klass was a guest reporter on BBC One's popular Sunday morning religion and ethics show Heaven & Earth with Gloria Hunniford. Klass's report, billed as the feature of the week, was on the Pope's astronomer. From 10 October 2006, Klass co-presented LIVINGtv's Ghost Towns beside popular medium and ex-Most Haunted star Derek Acorah. In May 2007, Klass appeared on Sky HD's Test Card.
Klass took part in the sixth series of ITV's reality television series I'm a Celebrity...Get Me Out of Here!, which began on 13 November 2006 and ended on 1 December 2006. She finished in second place, behind Matt Willis. Klass's brother Don, noticing his sister's popularity with the male audience, suggested she auction off her now famous bikinis from the show on eBay. Within a week of leaving the jungle, Klass took his advice and put her white bikini from the show on auction on eBay until 7 December 2006. Klass pledged that all the money raised from the auction would go to charity to help victims of the Farepak savings scandal. The auction raised £7,500.
In February 2006, Klass began presenting the Sunday Breakfast programme on Classic FM, taking over from Aled Jones (who returned to this slot in 2016). She worked for several years on the station's early morning show on Saturdays and Sundays and currently presents the Saturday and Sunday evening Smooth Classics programme (10 pm – 1 am). While working on the weekend morning show for Classic FM, she was also heard on London's Capital Radio on Sunday evenings from 8 to 10 pm. This show was also broadcast on GCap Media's One Network local commercial radio stations around the UK.
In early 2006, Klass was cast as one of the three women starring in the long-running play The Vagina Monologues and performed in Bromley, Richmond and Brighton. Her run was then extended to include all dates in Nottingham. Olympic champions joined Klass on 13 December 2006 to launch Lucky Dog, a new London 2012 National Lottery scratchcard. In 2008 Klass began designing a range of baby clothes for Mothercare called Baby K. Klass also writes a regular blog for the pregnancy and parenting website Gurgle, which is owned by Mothercare. Klass is the official godmother of the cruise ship Carnival Splendor. Klass is an EDF Energy / Team Green Britain Ambassador and took part in the launch of the EDF London Eye on 27 January 2011. In 2011, Myleene Klass began working with children's shoe brand Start-rite, helping the company design and promote a range of fitted footwear.
In May 2006, Klass was involved in a go-karting crash at a charity race in Cardiff, South Wales, sustaining an injury to her leg.
Klass has been an amateur astronomer for most of her life, having been taught the basics by her father. She was one of a handful of celebrities, engineers and scientists who were at the UK National Space Centre control centre for the touchdown of the UK Mars probe Beagle 2 in the early morning of Christmas Day 2003. Since then she has been a keen supporter of the UK's work in the European space programme. In March 2006, Klass publicly criticised the proposed closure of the London Planetarium and explained on television how to view Venus in the early morning. She also appeared on Channel 4's Richard & Judy to discuss the book Moondust, which follows the lives of the first men on the moon, and in 2007 attended the televised party on BBC One, held at the home of Patrick Moore in Selsey to mark the 50th anniversary of Moore's monthly programme, The Sky at Night. Klass once studied astronomy with the Open University.
On 15 July 2006, as part of BBC One's Sport Relief charity spectacular, Klass appeared as a special guest in the Question of Sport Relief segment. Klass's appearance involved her playing a variety of TV sport theme tunes on a grand piano. This part of the fundraiser was based on the BBC's popular A Question of Sport quiz show and was hosted by Sue Barker. Guest panellists on the show included Nancy Dell'Olio and Zara Phillips, who played alongside the regular team captains Ally McCoist and Matt Dawson.
During December 2006, Klass also appeared on The Big Finish with Graham Norton, in which she competed alongside Bill Oddie and Big Brother star Nikki Grahame for the "Showbiz" team (against "Soap" "Sport" "News" and "Judges" teams) to compete to win £10,000 for the winning team's chosen charities. However, the Showbiz team, represented by Graham in the final round, was beaten by the Soap team represented by former EastEnders actress Wendy Richard. In November 2007, Klass guest-presented BBC Children in Need and performed Your Song with John Barrowman. She also collaborates with Norwood, a Jewish charity for children.