| mi toki jan. | I talked about people |
The "about" is simply implied by the sentence. Now here's another sentence which is correct and in which pi is used to mean "about":
| mi toki pi jan ike. | I talked about bad people. |
The reason that pi can be used here is because jan ike is its own singular, individual concept, and the combined phrase (jan ike) acts on toki as one thing; pi is simply used to distinguish the jan ike phrase. If you left out pi, both jan and ike would become adverbs, and the sentence would mean something really strange like "Humanely, I talked evilly."
The word immediately after the pi must have another word that describes it.
Another mistake is that people use pi when they should use tan:
| mi kama tan ma Mewika. | I come from America. |