The 40-year-old actor will make his CBeebies debut on 25 June when he reads Supertato, a story by Sue Hendra and Paul Linnet, about a superhero potato and a supervillain pea.
The Night Manager star starts by saying: “Tonight’s bedtime story is all about a supervillain. This guy is really naughty, very cheeky… and bright green.
“But never fear, because where there’s trouble, a superhero is sure to follow.”
Hiddleston is reprising his role as the God of Mischief in the much-anticipated standalone Disney+ series Loki, which began streaming the first of its episodes last week.
He has played the antihero in Marvel’s big-screen blockbusters including Thor, Avengers: Infinity War, and Avengers: Endgame.
TV presenter Cat Deeley has also signed up to read a story, which will air on Father’s Day in the UK.
The 44-year-old will read Love Makes A Family, by Sophie Beer, a story all about the love shared by family members, on 20 June.
She said: “I love reading to my boys and they equally love watching CBeebies, so I was thrilled to be invited and actually get to read a real story this time.
“We had lots of fun on set with magical unicorns and dancing vegetables but, thankfully, no giant Geordie koalas!”
The TV star was recently reunited with her former SM:TV Live co-hosts, Ant McPartlin and Declan Donnelly, on ITV’s Saturday Night Takeaway.
Deeley was pranked during filming for what she thought was the reading of her children’s book, The Joy In You, for the CBeebies story slot.
Donnelly wore a disguise in his role as the shoot director while McPartlin donned a giant koala bear costume.
Hiddleston and Deeley are latest in a string of stars to have read a story on the children’s programme.
CBeebies Bedtime Stories airs each weekday at 6.50pm on the CBeebies channel and is also available on BBC iPlayer.
Watch: Loki cast talk to Yahoo about the Disney+ show