The first urine is discarded because it was made before the collection period began. It holds urine that built up in the bladder overnight, so counting it would add an unknown amount of earlier output to the 24-hour total.
I ran a quick PubMed check for recent systematic reviews. The only relevant one is a 2026 review of how 24-hour urine collection is done and reported for kidney stones (
PMID 41468103), which notes that methods vary. I did not read it in full, so I can't say whether it changes the standard instruction to discard the first void.