Sergiy Stakhovsky, a tennis player for the Ukranian team, has been given a gun and hopes he won't have to use it.
A three-weight champion boxer, who is also a sports star, has been photographed with a rifle.
Oleksandr Usyk is also thought to have signed up.
I know how to use the gun. If I have to, I will.
The 36-year-old retired from tennis after the Australian Open in January and has returned to help his nation.
Usyk left his London base to return to his home in Ukraine.
The 35-year-old is shown holding a weapon in the photographs on IG.
In a post on his Facebook page, the man was shown wearing a military uniform and carrying a rifle.
Men between the ages of 18 and 60 have been told by the Ukrainian government to stay in the country and fight as it looks to slow Russia's attacks.
I hope that I don't have to use the gun, I'm a former world number 31," Stakhovsky said.
The decision to leave his wife and children at their home was horrible.
He thinks Anfisa told their children that he went to a tennis tournament.
I'm not sure how I did it. I know that it is very hard on my wife. He said that his kids don't know that he's here.
They don't understand war. They are too little to understand what is happening.
The sporting organisation imposed sanctions on Russian teams and athletes after the country launched a military invasion of Ukraine.
On Monday, Russian football clubs and national teams were suspended from all competition until further notice.
The Russian men's and women's teams will not be playing in the World Cup play-offs next month and the women's team will not be playing in the European Championships this summer.
Spartak Moscow has been kicked out of the Europa League and Uefa has ended its sponsorship with Russian energy giant Gazprom.
The IOC wants sport governing bodies to ban Russian and Belarusian athletes.
The Ukrainian Tennis Federation wants the International Tennis Federation to ban Russia from team and individual tournaments.
Elina Svitolina said she will refuse to play Russian or Belarusian players until they are classified as neutral athletes.
The moves will make a lot of difference in terms of perspective for Russian President Vladimir Putin according to Stakhovsky.
He loves that Russia is successful in sport. During the Olympics and all the other sport events, he loves that he can demonstrate his success in the world.
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