'What was it about?' is the more normal phrase. This can refer to the subject of a conversation, a story, a film - almost anything. You wouldn't use 'on' in these cases.
'on' is used more in studying and business, to refer to the topic of a reference book, a lesson, a lecture, a seminar, a conference, or similar. So if your colleague at work went to a seminar, you might say 'What was it on?' ie what was the topic? If you see a classmate studying an academic book, you might say 'What's it on?'. But you could also say 'What's it about?' in these two cases.
Or in other words, if you are not sure, always use 'about', because it's a more general question.