It's possible that it's meant to be:
* "Chilling like a villain": This would imply relaxing and enjoying oneself in a way that is perceived as cool, mischievous, or even slightly dangerous, like a villain in a story.
* "Chilling like a valiant": This would imply relaxing in a way that is brave, noble, or courageous. However, this usage is not common and may be a playful twist on the word "valiant."
Without more context, it's difficult to definitively understand the meaning. If you heard this phrase used, it would be helpful to know where and how it was used to get a better understanding of its intended meaning.