Arithmetic functions now support 64-bit datatypes. There's also a suite of performance enhancements for some of the math users rely on heavily, including the 3-output form of svd, trig functions with degree inputs, and sparse column assignment.
MATLAB now supports arrays of timeseries.
There is support for classes that define Enumerations.
VideoWriter allows creation of AVI files on all platforms. And there has been a suite of updates to the HDF4, HDF5, and netCDF sets of functionality.