Here a brief intro for those that aren't familiar with DevOps:
http://www.jedi.be/blog/2010/02/12/what-is-this-devops-thing-anyway/
Before being introduced to the concept of DevOps, we at Twilio struggled with what to call the role. It requires a different kind of thinking. To us, DevOps is about automation to improve productivity, reduce risk, and achieve scale. DevOps engineers should always be striving to deprecate themselves. It has been more then 2 year since we founded Twilio and we've never had a sysadmin or an ops person. This has forced us to write better software automation from day one. However, having someone that can provide leadership on DevOps issues (and fundamentally understands distributed systems/CAP/etc) to the whole team is extremely valuable.
Configuration management tools like Chef and Puppet are the beginning but a more complete view of infrastructure and service automation (e.g., http://redeyemon.sourceforge.net/) seems inevitable in the long term.
We are looking to hire a Lead DevOps engineer. Here is the detailed job description if you know someone that might be interested:
http://twilio.jobscore.com/jobs/twilio/devops-engineer/bSHjYWq2Sr37U6eJe4aGWH
Call it what you will, 'DevOps' is just what you'd expect a good sysadmin to do in a sufficiently large org. That there is on going friction between developers and sysadmin ("it works on my box" is a valid excuse?) is perhaps a larger sign of the culture and people involved.