It took a while (a long while, in fact) before OpenOffice/LibreOffice got the whole printing-an-envelope thing down. In the bad old days it was ridiculously difficult to do because you actually had to create your own envelope template from scratch. Thankfully, it’s easier now, but the way it’s done still may confuse a few out there, so here’s how to go about it.
I’m not going to get into custom templates or anything like that. The goal of this tutorial is simply to print an envelope out of LibreOffice Writer as quickly as possible.
What is LibreOffice? A free alternative to Microsoft Office. The tutorial below assumes you’re using the latest (at the time of this writing) version 3.5.1.
Step 1.
Launch LibreOffice Writer to create a new document.
Step 2.
Click Insert and then Envelope.

Step 3.
The "Envelope" window pops up, and will have the tabs Envelope, Format and Printer. By default you will start on the Envelope tab. Fill out the appropriate information:

The Format tab adjusts positioning.
The Printer tab is where you can set an envelope type if you wish. See next step.
Step 4. (Optional)
A common complaint with the way LO does envelope printing is, "Where can I select the envelope type?" That’s done via the Printer tab on the window you’re still on:



All the envelope types are there. What LO does is give the printer control over the paper size instead of handling it directly within the document editor software itself.
Important note: If printing standard sized envelopes, you shouldn’t have to do any of this. But if you encounter problems with sizing, now you know where to change the appropriate settings.
Step 5.
When done, click the New Doc. button (from the Envelope window):

If you don’t do that and click Insert instead, what happens is that Writer will create your new envelope along with a single blank page. Since we don’t want that blank page, use New Doc. instead. Yes, this will create a second document, but it’s worth it to avoid the blank page crapola.
You’ll end up with something that looks like this:

From here you can adjust fonts and sizes of fields.
For field adjustment size, just click on a field area border. Green boxes will appear which are "grabber points". Your mouse cursor will change to a sizing arrow whenever you hover over one of them. From there, click-and-drag to whatever size you wish:

Step 6. File > Print
When you click File and then Print, you will once again have the option of checking to make sure you have the correct size selected:
The left portion will tell you what envelope size is selected:

The right portion has a properties area where you can select a different size, if need be:

For example, maybe you want to select a standard Envelope #10. The Properties area is where you do it:

After that, click OK, then Print:

…and that’s it.

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I stumbled onto this myself eventually, but was still never able to print it out correctly. The printer would only print the addressing in landscape no matter what. I finally gave up and exported it to pdf where adobe printed it out correctly. I don’t think Libre Office will ever be ready for prime time.