This a hard question to pose. There's different types of defense. Some fighters have the shield like Winky Wright, some use their legs to get out of the way Like Roy Jones, some slip on the inside like James Toney, some use excessive clinching like Wlad.
There's a lot of great defensive fighters in the history of the sport. Off the top of my head, the true standouts were: Benny leonard, Willie Pep, Nicolino Locche, Wilfred Benitez and Floyd Mayweather Jr. These are in my opinion the 5 greatest defensive fighters in the history of the sport. You can make an argument for 2 or 3 of those guys being the very best ever. FLoyd has some of those great accolades that only come with being an ATG defensive fighter- he's never been knocked out in a fight, his opposition continually lands less than 20% of their punches on him, he's had a very long and undefeated reign in 5 weight divisions and is still considered the best P4P fighter in the sport into his late 30's. Those are some of the elements of his resume that some of the other great fighters I mentioned never had (I won't go into level of competition however.) Whitaker is similar to FLoyd, but Mayweather took much better care of himself between fights and also is a bit more serious in the ring (Pernell was such a skillful fighter that he would at times toy around a little too much with his opposition.) From a neutral perspective, I can't see how Mayweather isn't considered a top 5 defensive fighter ever. He's done enough IMO to deserve that consideration.
Watch some Miguel Canto, Hilario Zapata, and Miguel Lora fights if you want to see great defense with style.