It was speculated that Penn, 53, and Theron, 38, were serious about each other and he had apparently popped the question to her recently, reported People magazine.
The couple were spotted together in January at Penn's third annual Help Haiti Home gala.
The 'Prometheus' actress had sparked dating rumours when she was seen having a good time with Penn during a holiday trip to his beachfront home in Oahu, Hawaii, where they reportedly celebrated the New Year together.
Penn is allegedly planning to direct Theron in a love story, 'The Last Face', which also stars Javier Bardem.
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