Pretty sure the trader and the innkeeper in Riverwood each had one to buy. If you wait 24 hours they may get another in inventory. I haven't joined the Thieves' Guild or even gotten out of Riverwood yet so I don't know who else has them.
Also, if you are of the dishonest variety (and who looking for lockpicks isn't), it seems like nearly everyone has a lockpick on them when I pickpocket them. Bandits are a great source of lockpicks as well.