It’s hard to think of a worse cover than “Peace Corps volunteer.”
Being a Peace Corps volunteer is to experience the most astounding lack of privacy. In Cameroon, I’d often wake up to the small faces of curious children pressed against my window, wondering what I was doing so late on a Saturday morning. If I received a guest, I could expect my neighbors to come over with food (can’t have guests going hungry, and god knows what that nutty foreigner cooks) within half an hour- and I’d hear questions about how my “sister” or “brother” is doing for months after. If the guests were foreigners, usually a kid would spot them on the road into town and come breathlessly to my house to announce the unusual event. I’d often visit my neighbors and find their homes festively decorated with the Doritos wrappers and powdered milk cans I so carelessly tossed in the trash. If I wanted to buy a beer, I’d have to carefully conceal it in my bag as I walked home unless I wanted to hear all about how scandalous it was for the next week. When my house was robbed, the police had heard all about it by the time I made it to the station to file the report. It was hard enough to, say, go on a date without the entire village gossip mill going on overload. I can’t imagine trying to actually do something clandestine.
Even as a volunteer in China, I’d often meet people and hear “Oh, I know you! I saw you once last October at the grocery store buying cold medicine! You were wearing a red sweater. I told all my friends about it!” Once, I left my sweater in a taxi, and the next day I got a mysterious phone call wondering where the taxi driver should drop it off.
Another complication is that volunteers generally have work to do, and people will notice if you are not, say, going to farmer’s groups meetings and are instead making lots of strange phone calls with mysterious strangers. Real spies have fake jobs that nobody expects to be done. Peace Corps volunteers will be very, very noticed by everyone in town if they are shirking their duties. No spy wants to spend all day teaching English grammar or supervising latrine installations.
Then there is security. After my house got broken into, my security was a 16 year old kid named Divawissa who would take a break from his job selling honey at the local market to watch my house when I taught classes in order to discourage the neighborhood punks from breaking in to try on my Chacos and wear down the battery on my shortwave. The kind of security someone with something to protect would need would be very conspicuous in a Peace Corps setting (and much less so in a diplomatic or business setting).
Finally, the places where volunteers go are generally not particularly interesting. My Cameroonian village thought I was a spy, and I always wondered what they thought I was reporting. Maimouna is mad that her husband gave a radio to his second wife? There was a minor scuffle at the market over the price of follare leaves? Bouba thought his dog had rabies? And my contacts were not politicians and the like, but rather school teachers, market ladies and street kids. The chances of having useful intelligence is slim.
In short, it’s not practical. Even if it were, Peace Corps does a very good job of fulfilling its soft diplomacy goals, and there is no benefit to endangering that (and all of Peace Corps would be over and all of it’s work tainted forever if a spy were caught) when there are plenty of perfectly good covers out there that aren’t going to have those problems.