OK, so I accidentally discovered something tonight which has me a bit puzzled.
I was experimenting with my settings this week and I left the camera in Av mode instead of M by mistake, and found that my 622s weren't triggering reliably. All other settings including flash sync (1/250 fixed), aperture (f/5), AF, ISO, etc. etc. are identical as it happens. I was using my 17-55IS. The 622s were set as ETTL A:B with about 4:1 ratio; there are two YN565 units about 30 feet from the target in different directions, firing roughly at right angles to each other; each in a YN622 hot shoe. A LOT of shots only had one flash triggering - or else the other flash was so low as to be invisible. The frames were, by examination and by looking at the histogram, underexposed. Once I realized what I'd done and went back to M, everything was great again. I did some testing afterward and Av mode was very inconsistent. Yes, I factory reset the YN622s to be sure.
So I know that ETTL is geared toward fill flash, but there was minimal ambient in the venue; in fact, at 1/250, f/5 without flash, the frame was essentially dark (I tested). So it wasn't ambient lighting fooling the algorithm. But whether in M or Av, I was using essentially the same camera settings because of the fixed flash sync speed. Is there something about Av mode on Canons that causes ETTL to prefer one flash over another, regardless of the ratio settings? Or is there something else going on?