TextAloud doesn't currently allow you to open WORD .doc files directly. This should be coming in version 2.0 later this year. For the moment you have a few options to handle them.
1) Saving as .txt file
In Word, you can do File->Save As, and save the contents of the document as a .txt file, which you can then open in TextAloud using File->Open on the TextAloud Main Menu.
Using TextAloud's clipboard watching features, you can highlight text, then hit control C to copy the text to the windows clipboard, where TextAloud can automatically grab it.
TextAloud Hotkeys can be setup via Options->HotKey Setup. Give the Speak hotkey a try first. Set it to something obscure so other programs that use global hotkeys don't intercept the signal. So for the Speak hotkey, set it for Control-Alt-Shift-Z then close that window. You can minimize TextAloud to put it back to the system tray. Then, in any program, highlight some text and hold down the Control, Shift, and Alt keys then press Z. TextAloud will automatically begin speaking the highlighted text.
After you get this one working, experiment with the others. These give you a great way of interacting with TextAloud without using the clipboard.