The 30-year-old opted for a vintage Christian Lacroix pearling and vermilion tunic dress and Rene Caovilla strappy sandals as she tried to score fashion points with her 1920s look.
But the dress was poorly chosen for her rapidly thinning frame - and its low cut exposed her bony breastplate and almost non-existent cleavage.
Working the red carpet: Katie Holmes looked super skinny as she joined Tom Cruise at the Rio de Janeiro premiere of Valkyrie
The actress appears to have lost a lot of weight recently and the unforgiving cameras in Rio quite clearly caught her protruding collarbone and bony spine, while her modest décolletage was lacking support of a bra and exposed her sternum..
While her figure looked thinner than ever, Katie made sure she lost the pale look she has sported in recent days with lashings of red lipstick and smoky eyeliner.
The star of the show, husband Tom, looked suitably dapper in a black suit and white shirt as he attended the Rio de Janeiro screening of Valkyrie, a drama about the failed assassination attempt on Adolf Hitler.
Katie's frame has been getting noticeably slender since she moved to New York for her Broadway run last year.
Too thin: Katie's bold Christian Lacroix dress and dramatic make-up couldn't distract from her protruding collarbone and bony back
In the last few weeks of her gruelling run in the production of All My Sons, which finished on January 11th, Katie was spotted looking pale and drawn when photographed outside theatre.
In December, Katie was spotted carrying a bottle of cult drink Celsius, which claims to contain a ‘thermogenic blend’ which increases metabolism in order to burn calories.
Each bottle contains less than 10 calories and its makers claim that it can burn up to 77 calories over a three to four hour period.
Earlier on Tuesday, Katie brought Suri to Rio de Janeiro's famous Copocabana Beach, while her husband was talking to the Brazilian press.
The beach is notorious for theft, so Katie was accompanied by several members of the couple's extensive security guards.
Mobbed: Tom was besieged by fans at the premiere
Dressed casually in a shorts and a short-sleeved sweater, Katie carried Suri's shoes as the toddler ran through the golden sand.
Meanwhile, a few blocks away, Tom was promoting his film to the country's press.
Falling victim to a few cultural misunderstandings, Tom thanked a journalist with 'Gracias' - thank you in Spanish, instead of the Portuguese 'Obrigado'.
The 46-year-old then said he enjoys the tango - the traditional dance of Brazil's neighbours Argentina - instead of the Samba.
The Hollywood couple and their two-year-old daughter Suri have been in Brazil since the weekend.
The week in Rio has given Tom the chance to relax after a gruelling promotional tour for the movie.
In the last few weeks, the Top Gun star has attended the film's premieres in London, Berlin, Moscow, Los Angeles, New York, Tokyo, Seoul and Madrid.
Beach babes: Katie and Suri stroll along Rio's famous Copacabana Beach
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