General antonyms:
* Free
* Independent
* Unconfined
* Liberated
* Unrestrained
More specific antonyms:
* Released (if referring to a prisoner)
* Wild (if referring to an animal)
* Self-employed (if referring to a worker)
* Autonomous (if referring to a system or entity)
The best antonym depends on the specific situation in which the word "captive" is used.