After some googling, it looks like there is indeed some support for ERB files in XCode. It's a little hidden, though.
Check this page out: ERB Highlighting. In brief, XCode is looking for .rhtml files instead of .erb files, so .erb files don't trigger the ERB syntax highlighting. The solution, then, is to go open
/Developer/Library/PrivateFrameworks/DevToolsCore.framework/Versions/A/Resources/Standard file types.pbfilespec
look for the mapping for rhtml:
Extensions = (shtml, jsp, rhtml);
And add erb to the list:
Extensions = (shtml, jsp, rhtml, erb);
Viola! Just restart XCode and you'll get erb syntax highlighting. There's probably a way to do it from within XCode itself, but I haven't found it yet.