My Rig: Phenom x4 965 O.C. @ 3.8, Formula IV Mobo, Radeon 5770 Stock, Corsair Dominator CL9 1333Mhz 4 Gig Ram

Settings: 1080p Resolution on 22.5" Monitor (Windowed)
General Drawing Highest (10), Background Standard(3). Shadows Standard.
Texture Quality High
Texture Filtering High
No DOF, NO AO

All my other Graphical Settings are set through AMD Overdrive.
Gaming Performance
Standard 3D Settings (Custom)
Mipmapping (Quality)

Image Quality
Anti-Aliasing - Morphological Filtering 8X Wide-Tent Samples 16X
Anti-Aliasing Mode - Super-Sample AA
Anisotropic Filtering 16X

With this I have smooth Gameplay 45-50 FPS

Since I was having such good luck using these settings playing FFXIV with great visual effects/FPS etc, I decided I would run the benchmark to see what kind of scores I was getting. Oh high I was getting 1500ish as a score. On Low I was getting 3000ish. Which was pretty confusing to me as you will see in a second.

AMD Overdrive. Setting "Use Application Settings"
Benchmark Low 4400, Benchmark High 3000

You might be saying, well then just keep it at "Use Application Settings"
Well for actual gameplay, I have better and smoother graphics using higher settings using AMD Overdrive, despite my Benchmark Score being cut in Half.

(Side Note) Using AMD Overdrive Graphical settings I am able to run Depth of Field and Ambient Occlusion through the FFXIV Config. Although I can only pull 20ish FPS on high settings. This is far betting than using "Application Settings" plus DOF and AO in which I only run 10FPS and find that the game is comletely unplayable.

In conclusion. Running AMD Overdrive over FFXIV Config settings gives a great Performance boost playing FFXIV despite the Benchmark score showing otherwise.

If anyone else running an AMD product Video Card would care to list their findings as well that would be great.