ITV is just like in 2013/2013 broadcasting Champions League matches online. During the Champions League weeks they broadcast one match every Tuesday, and you can of course watch it online without paying for it.
To be able to watch the Champions League match online on ITV, you need to be in the United Kingdom, at least virtually, meaning that you need a UK IP address. If you want to watch it like this, I have already written an article on how to watch ITV from abroad, and that is in fact the subject of this entire page, so if you just read around in the different articles available and click the link above, then you will find out how to watch Champions League matches on ITV online within a few seconds from now.
If you first follow those instructions, you should be aware of the fact that you can use the same strategy to watch lots of other Champions League matches as well, and you can read more about that in this article from the IP Guide on how to watch Champions League online.
Enjoy it, and my favorite to win the Champions League in 2014 is Chelsea. Do you have a favorite?