5. Greg Maddux - 66.2 WAR
Greg Maddux being on the list is hardly surprising. What is more surprising is that he is only #5. In 11 seasons with the Braves, Maddux posted a 2.63 ERA and 2.95 FIP while walking just 1.4 batters per nine innings pitched which is absurd. He won three straight Cy Young Awards (four if you include his hardware from the Cubs), finished in the top 5 an additional four times, and was a perennial All-Star and Gold Glover.
For many, Maddux would be on all of baseball's Mount Rushmore of pitching and he has a strong argument for it. However, he "only" accumulated 66.2 of his 106.6 RWAR with Atlanta as he spent nine-plus seasons with the Cubs along with a handful of seasons with the Dodgers and Padres as well. Fortunately, he was so awesome with the Braves that he was still able to put up enough production to make it on the list comfortably in fifth place.
4. John Smoltz - 66.9 WAR
Coming in at #4 on the Braves' all-time starting rotation is John Smoltz. Part of the Braves' Big Three throughout the Braves' epic run in the 90's and early 2000's. In 3395 innings with the Braves from 1988 to 2008, he struck out 3011 batters and posted a 3.26 ERA which is crazy when you consider how long he played. His finest season came in 1996 where he won his only Cy Young with a 2.94 ERA and 2.64 FIP with 24 wins on his ledger.
Smoltz probably couldn't have gotten higher up on this list simply because of the gap between third and fourth, but he absolutely could have added significantly to his WAR total if arm trouble didn't push Smoltz to the bullpen from 2001-2004. However, Smoltzy was still fantastic as a reliever with 7.4 rWAR and 154 saves in 246 appearances during that span. He would eventually return to the Braves' rotation, but Smoltz would leave before the 2009 season to sign with the Red Sox.
3. Phil Niekro - 89.6 WAR
The battle for spots 2 and 3 was close, but Phil Niekro takes home the bronze with 89.6 rWAR with the Braves. Niekro's name is mentioned often as one of the greats to be sure and he is fondly remembered as the best knuckleballer of all time, but folks don't appreciate just how good Knucksie really was. From 1964 to 1983, Niekro threw 4619.1 innings with the Braves and posted a 3.20 ERA and 3.45 FIP with a staggering 226 complete games along the way. Niekro wasn't ever able to win a Cy Young, but he did finish in the top six a total of five times.
Funnily enough, Niekro would have come in second on this list if he had played his entire career with the Braves, but his 7.6 rWAR from 1984-1986 came with Cleveland and New York. However, if that was how this list worked, then Maddux would have been much higher and Spahn (spoilers) would have added some production as well, so it sort of all worked out in the end.