Hmm… this one is actually trickier than it seems.
Probably for the most memorable? Probably WotLK fits the bill. It’s definitely the “biggest jump” in terms of overall quality relative to the previous expansion (Vanilla and TBC weren’t really much to look at, but you were used to the structure after so long). We have several memorable events like all the run-ins with the Lich King, both inside and outside dungeons. Storylines finally became compelling, and we had tour-de-force moments like the Wrathgate and the subsequent Siege of the Undercity scenario (sadly removed for quite a while now). The Stormpeaks also had amazing moments like the Drakkensyrd (hopping from proto-drake to proto-drake), all the mysteries surrounding Ulduar… and again, the Lich King serves as a unifying force for all of it. We also have technical improvements like phasing and group scenarios (Assault on Light’s Hope in the DK starter zone and Siege of the Undercity), which pre-dated actual scenario instances and solo scenarios. It was a MASSIVE improvement… for the time.
Sadly, it hasn’t aged well at all… and one of the best parts was removed (Siege of the Undercity again) for some dumb reason. Nevertheless, it laid the foundation for better leveling experiences going forward… and for the time, it was some of the best leveling you could experience.
In the more modern era, things are generally better. As noted above, WotLK feels too dated now even though it could still arguably be the best in terms of content… but the pacing and mechanical details really don’t mesh well with the game.
From the modern era, I’d put it towards MoP. From that point on, the quality of the leveling experience (in terms of pacing and mechanics) has pretty much plateaued; it’s all very good, but there hasn’t been any huge innovations or changes since then.
So we start looking at things like character, personality, and content… and to that end, MoP has a charm that no expansion before or since could ever hope to match. WoD tried too hard to be dark and gritty. Legion confined it’s best zone (Suramar) to the level cap, so it kind of gets ruled out on a technicality here… but even then, I’d lean slightly towards MoP. BfA, even if you ignore the MAJOR issues with the level cap content, can’t quite live up to the standards set by the previous three expansions.
MoP had a heart, a fun spring in its step and knew when to take a somber tone… giving it some of the greatest highs and lows in any expansion.