Dominating the race from the start, Ledecky fended off a late charge by Australia's Ariarne Titmus to win gold in 8:12.79 - the 17th-fastest swim of all-time and of her career.
Titmus, having bettered Ledecky in their 200 and 400 freestyle duels earlier in the week, lowered her Commonwealth record by almost two seconds to claim silver in 8:13.83.
Grimes, the second fastest qualifier into the final following her teammate Ledecky, was unable to replicate her heat time and settled for fourth place in 8:19.38.
Outside the 8:20 club, China's Wang Jianjiahe (8:21.93) and Titmus's teammate Kiah Melverton (8:22.25), picked up the fifth and sixth spots respectively, finishing 31-hundredths of a second apart from each other.
Up to one swimmer per NOC meeting that time was eligible for selection, allocated by world ranking until the maximum quota for all swimming events was reached.