What problem you are facing in doing so??
Just use PIC Micro-Controller UART and RS232 Line Driver IC such MAX3232/MAX232 to send data on PC, instead of receiving on Hyper-Terminal program of windows, use MATLAB to receive data.
First of all you have to Open the Communication Port.
The Following Command Creates a Serial Port Object associated with COM1 and will set its Baud Rate = 9600 bps
s = serial('COM1','BaudRate',9600);
Then you have to open this port, the command is as follow:-
To Send a String to RS232 Port:
To Receive Data from RS232 Port in MATLAB
To Close the Port
I am also attaching some links with tutorial on MATLAB Serial Based Communication, apart from that refer MATLAB Documentation, everything is properly explained in that document.