Well, 'the greatest', I'm not sure of (386 was also a huge leap, and 286 was not bad either), but the Pentium was indeed a huge leap forward.
It mainly had three rather revolutionary changes compared to the 486:
1) It had a 64-bit data bus instead of 32-bit, so it could access memory twice as fast.
2) A superscalar architecture, meaning that it actually has two execution pipelines that can work in parallel, where earlier CPUs only had one pipeline. Best-case your code could literally run twice as fast as on a 486, because it pretty much was as if you had two 486 CPUs running side-by-side.
3) A much much much much much faster FPU.
This makes that on well-optimized code, a Pentium 60 can indeed outperform a 486-100 with ease.
For me personally it is the nicest x86 to write assembly code for. It is the last in-order execution architecture, so the last x86 to execute code exactly the way you write it. There is a certain elegance to ordering your code to maximize the use of the U and V pipelines.
The Pentium Pro was also a big leap, but not in terms of performance... at least, at first.
The architecture allowed much higher clockspeed scaling though, which means that we went from the ~200 MHz limit of the Pentium to 1+ GHz in a record time (Pentium II and III used the same basic architecture as the PPro, with MMX and SSE added, and some advances in manufacturing).
The original Athlon isn't a big tech jump, it's pretty much a clone of the Pentium Pro architecture.