The phrase carries negative emotions and indicates harshness in someone's personality. He dismissed their pleas without remorse; he must have a heart of stone.
Pro Tip 2/3
Metaphorical Use
It's not literal — nobody has an actual stone heart. It's a metaphor for lack of empathy. I can't believe she just laughed at his misfortune. She has a heart of stone.
Pro Tip 3/3
Character Assessment
Used to judge character, often indicating surprise or disapproval at one's cold behavior. Even though he's rich, he never donates to charity. He has a heart of stone.