Decaf coffee, how to make our own I saw this on a coffee site:  


  As we all know, it is really hard to get a good decaf specialty
  coffee. The decaf process removes oils and flavors as well as the
  caffeine, leaving a blah cup behind. It's a little known trick that
  you can "decaf" your coffee using a french press. Pour just enough hot
  water to cover the grounds. Let sit briefly. Press the grounds and
  pour off the water. As caffeine is highly soluble in water, this first
  extraction should pull off most of it. Then add more water to the pot,
  and extract as usual. Voila! A ‘decaffeinated’ coffee.


Is there any validity to this?  Are you just tossing out good coffee or does this actually work?  Many thanks.
In short: Very probably, you will lose the very best part of your coffee.

Caffeine is highly soluble, yes. But, also the other lipids and aromatics, too. So, you cannot obtain the benefits of specialty coffee if you ruin that first brew. The main taste we gain from coffee grounds are received from the soluble aromatic oils in the coffee. You don't want to loose them by pouring.

Normally, decaffeination process is made when the beans are green. That's why the aromatics are kept inside the beans when the beans are over-hydrated and then dried (in the Swiss process, which is the common way recently) a few times in a cycle to near completely remove the caffeine.

You can check the decaffeination process in the following question:


How is decaffeinated coffee made?


And also watch a nice explanatory animation here.

Still, if you wonder how to use the grounds for a second time, please see this discussion:


Brewing with the same coffee grounds twice?