1. In the MATLAB Command Window, execute the following commands:
cd(matlabroot)
cd bin
edit mexopts.sh
2. Save a backup copy of this file somewhere in case you make a mistake and you need to revert your changes.
3. Scroll down to the Mac (“maci64”) section of this file, beginning around line 120.
4. Replace all instances of 10.7 with 10.8; there are four of these in all (a fifth may be found in comments only)
5. Save the file, then execute the following command in the MATLAB Command Window:
mex -setup
Source: http://www.mathworks.com/matlabcentral/answers/103904-can-i-use-xcode-5-as-my-c-or-c-compiler-in-matlab-8-1-r2013a-or-matlab-8-2-r2013b