Yes. Click the settings button and select the profile from which you want to print an envelope. Click the envelope button on the settings dialog box button. Another dialogue box as shown below will appear:

Check the box to enable envelope printing and select the printer you want the envelope to be sent to. Also select an option to state if you want the envelope dialogue box to be shown before or after the main printing. Click OK.

Now, when the profile button is pressed it will also show the normal Word envelopes dialogue box allowing you to print an envelope too. Note that the printer used for envelope printing will be the one you selected. The tray used can be changed within the envelope dialogue box, and once you have selected the printer tray you want to use, this will be remembered for all future envelope printing jobs.