Ask questions about his expertise and experience in applying MATLAB in your domain.
Ask questions about how he would approach designing an application for implementation in MATLAB. If he refers to recent features of MATLAB, ask him to explain them, and how they are different from the older features they replace or supplement, and why they are preferable (or not).
Ask questions about his expertise with MATLAB data structures. Many of the MATLAB 'experts' I've come across are very good at writing code, but very poor at determining what are the best data structures for the job in hand. This is often a direct consequence of their being domain experts who've picked up MATLAB rather than having been trained in computerism. The result is often good code which has to compensate for the wrong data structures.
Ask questions about his experience, if any, with other languages/systems and invite him to expand upon his observations about the relative strengths and weaknesses of MATLAB.
Ask for top tips on optimising MATLAB programs. Expect the answers: vectorisation, pre-allocation, clearing unused variables, etc.
Ask about his familiarity with the MATLAB profiler, debugger and lint tools. I've recently discovered that the MATLAB 'expert' over in the corner here had never, in 10 years using the tool, found the profiler.
That should get you started.