Of course, it did (and continues to be used widely). The earliest potential arrow heads date from about 64,000 years ago in the South African Sibudu Cave, though their identification as arrowheads (as opposed to spear or dart heads) is uncertain.

However, here is a photo of a pitched battle in Kenya recently after local elections. Maasai warriors clash with members of the Kalenjin tribe on a hill overlooking the Olmelil Valley. The battles follow codified, age-old traditions. You can find the album about the story here.

San hunters also kill their game using arrows and spears tipped in diamphotoxin, a slow-acting arrow poison produced by a beetle larvae.

I grew up in West Africa, and I know it was quite widespread albeit specific to certain professions.