I think it would be easier to use LabVIEW than Matlab to interface your microcontroller to PC .
However, if you insist on using matlab, there is an interconnection between LabVIEW and Matlab where the data acquired from your pic chip to LabVIEW can be exported to matlab and can be processed there.
I don't think you could directly use matlab to communicate with your chip.
Better you check in google.