Yes, it is totally possible to intercept Word commands. In the VBA days, it was as easy as creating a macro with the same name as the internal Word command.
In VSTO, you need to add the command overwrite to your Ribbon XML and then add a callback to your code.
The entire procedure is described in MSDN: Temporarily Repurpose Commands on the Office Fluent Ribbon
Sample Ribbon XML (overwriting the standard Save command)
<customUI xmlns="http://schemas.microsoft.com/office/2006/01/customui"
onLoad="OnLoad" >
<commands>
<command idMso="FileSave" onAction="mySave" />
</commands>
<ribbon startFromScratch="false">
<tabs>
<tab id="tab1" label="Repurpose Command Demo" >
<group id="group1" label="Demo Group">
<toggleButton id="togglebutton1"
imageMso="AcceptInvitation"
size="large"
label="Alter Built-ins"
onAction="changeRepurpose" />
</group>
</tab>
</tabs>
</ribbon>
</customUI>
Ribbon Callback
public void mySave(IRibbonControl control, bool cancelDefault)
{
MessageBox.Show("The Save button has been temporarily repurposed.");
cancelDefault = false;
}