Having just installed Mountain Lion on my MBA, I encounted a few small problems while trying to install RVM as well as Ruby, etc. Below are the steps I took to get Ruby on Rails up and running on my new Mountain Lion install.
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Step 1. Install XCode (this isn't required but it's best to install it)
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Step 2. Install the XCode Command Line Tools from developer.apple.com. Note you need to download the 10.8 command line tools which is at the bottom of the list on XCode 4.4. I made the mistake of downloading the 10.7 Lion set first!
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Step 3. Install XQuartz