Salary and Such
Working at Peace Corps is similar to working at any federal agency in the U.S. The pay scale and benefits are the same and you are a bona fide employee of the federal government. It is just like any other government job in these respects (including being furloughed when Congress can't pass a budget).

But ...
There is one major difference that makes Peace Corps different from other federal agencies. The Peace Corps has what is termed "The Five Year Rule". The maximum consecutive years you can work at Peace Corps is set at five years. While there are sometimes extensions allowing people work an extra one or two years it is rare.

As an employee you are appointed for a 2.5 year tour which is usually, but not always, renewed for another 2.5 years. At the five year mark that's all - it's a congressional mandate and non-negotiable. To make it a bit easier to secure another job you are given non-competitive eligibility for one year. If you really like having a job at Peace Corps you can compete to be hired again in five years (or if you leave after three years you have to wait three years to come back, etc.). It's not uncommon for people to return to Peace Corps - a testament to the positive work environment.

What this means to the job seeker ...
The first implication is that jobs open up frequently at Peace Corps. You can imagine with nearly 20% of the staff leaving each year there are lots of job opportunities. And most Peace Corps staff seem to start looking for jobs after their third year. My guess is that the average time on the job is somewhere around 3.5 years, maybe less. Note that there are a few exempt positions such as safety and security personnel.

While this means frequent job openings, there is considerable competition. Peace Corps is a great place to work and lots of people are interested in a job there. Add in the people who previously held jobs potentially returning and you'll want put some time in writing your job application. But it's not impossible and is worth the effort.

Some notes about Peace Corps Jobs

How to Find a Job Listing a Peace Corps
It's actually fairly easy to keep up with openings at Peace Corps. Since new jobs come up frequently you'll want to set up a schedule to check or automated emails. If you have a USAJobs.gov account you can have all job openings with the term "Peace Corps" in the posting sent to you each week. You can also set a reminder in your email program to check each week the Peace Corps website for vacancy listings. There is also some good advice there on applying on the site as well.

Don't be discouraged if you aren't successful at first. Learn what you can, especially if you make it to the interview stage, and keep an eye on the job listings.