A glance at BBC Genome reveals that the first Champions League episode aired on 31 October 2000.
The 'Link was barely eleven weeks old at that point. In contrast, Pointless took
to make its way to primetime BBC1...
I believe the first Champions League episode was also the first to feature the familiar head-to-head stings, including the ascending four-note sting at the start and the descending one immediately preceding the first question. It took until August 2001 for these stings to make their way to the daytime version, however - here's a daytime episode from May with the original stings, as well as the original chain design with no pound symbols in front of the amounts below £1,000:
I prefer the second Grange Hill theme tune to "Chicken Man". Does that make me weird?