In a world where we had precision tools that could be used to deliberately alter brain morphology, the direction of causality would be highly relevant for trying to
treat ADHD -- it would tell us whether there is any point in trying to use those tools. But for diagnosis only, I don't think the direction is actually relevant. That is, if we see a strong correlation between ADHD behaviour (as measured by, say, a standardised written test) and certain brain morphologies, then we're justified in concluding that ADHD has some objective physical manifestation -- that is, that the written tests aren't just measuring arbitrary collections of symptoms, they're estimating "something real". There might still be many different underlying causes.
Would this be useful? I think so: It would then be possible to assess the accuracy of a written test.
I think the risk of conflation with stimulant use that another poster mentioned is very real, though, and that problem is a close cousin of the "direction of causality" problem.