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Musk directly called out the Russian president in a tweet, typing out Putin's name using the Russian alphabet.
"I hereby challenge Владимир Путин [Vladimir Putin] to single combat," he wrote.
Musk then added: "Stakes are Україна [Ukraine]," also writing out the country's name in its own language.
I hereby challenge- Elon Musk (@elonmusk) March 14, 2022
to single combat
Stakes are Україна
About 20 minutes before volunteering to take on Putin, Musk had also tweeted: "By the pricking of my thumbs."
The line comes from Shakespeare's Macbeth, and is used to allude to a sense of foreboding - followed in the play by the phrase: "Something wicked this way comes."
Shortly before that, the SpaceX billionaire had also cryptically tweeted: "There is a beauty to the biological substrate."
While it's not clear what he meant by this, the Independent reports that the phrase is often used in neuroscience and psychology - something Musk has expressed an interest in through his startup, Neuralink.
The 50-year-old recently answered Ukraine's calls for help by sending Starlink terminals to the nation.
Internet connectivity in Ukraine has been seriously affected by the Russian invasion, with Reuters reporting that southern and eastern parts of the country - where fighting has been at its heaviest - have been hit hardest.
According to the outlet, while satellite technology is costly to deploy, it can provide internet for people who live in rural or hard-to-serve places where fibre optic cables and even cell towers cannot reach.
At the end of last month, Ukraine's Vice Prime Minister Mykhailo Fedorov tweeted Musk to call on his help, writing: "@elonmusk, while you try and colonize Mars - Russia try to occupy Ukraine! While your rockets successfully land from space - Russian rockets attack Ukrainian civil people! We ask you to provide Ukraine with Starlink stations and to address sane Russians to stand."
Musk later replied: "Starlink service is now active in Ukraine. More terminals en route."
Starlink is a space-based system of satellites that SpaceX has been building for years to bring internet access to underserved areas of the world. It refers to its dishes as 'terminals'.
And he was true to his word, with Fedorov sharing a photo of the shipment and thanking Musk on Monday 28 February.
Commenting on the tweet, Musk responded: "You are most welcome."