First off the bad news. The bad news is that of the 16 pieces of armor that has expertise on it, 12 of them are leather or mail.
Even worse news: Not a single weapon with expertise has spell damage on it (not too surprised there...)
Which means there are only really 4 slots, and maybe a swap-in 5th slot that we can use to raise our expertise.
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First I'll touch on the three pieces available outside of the 25 man raids for those who don't have the numbers to go there:
Brooch of Deftness: Neck, 48 STA, 22 Hit Rating, 21 Expertise Rating
Acquired from: 35 Badges of Justice
Personal thoughts: While the lack of avoidance and defense is painful, if you can make up the loss elsewhere, it's got a lovely amount of Stamina, good hit rating for RD, and 5.04 points of Expertise.
Bracers of the Ancient Phalanx: Plate Wrist, 703 Armor, 45 STA, 23 Defense Rating, 22 Expertise Rating
Acquired from: 35 Badges of Justice
Personal thoughts: Due to the expertise, these are easily one of the, if not the best tanking bracers currently in the game. The expertise nets us 5.28 points of Expertise.
Shapeshifter's Signet: Unique Ring, 25 AGI, 18 STA, 20 Expertise Rating
Acquired from: Exalted with Lower City
Personal thoughts: One surprising change was this. Previously it had Dagger and Feral Combat skill bonus, making it primarily useful to Rogues and Feral Druids, now with the change this becomes useful to a much broader range of classes. Much like the Brooch of Deftness, it's value is based upon whether you can survive the loss of stats in other areas. Expertise rating gets us 4.8 Expertise.
Assuming you pick up and use the three items I've listed above you can get your Expertise up to the respectable levels of 15 points, or -3.75% chance to dodge and chance to parry.
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Now the following two weapons and pair of gauntlets are available in 25 man raids so they will be a bit harder to get.
Mallet of the Tides: Main Hand Mace, 1.7 Speed, 96.8 DPS, 34 STA, 16 Defense Rating, 14 Expertise Rating
Acquired from: The Lurker Below, Serpentshrine Cavern
Personal thoughts: The loss of spell damage makes this a costly option for full time use for a Protection Paladin, but as a swap in piece for more survivability during an extended fight, this is a great option. The Expertise Rating of 14 gives 3.36 Expertise. Additionally for a Human Paladin, using this will also give the racial bonus of 5 more Expertise.
The Brutalizer: One-Handed Axe, 1.6 Speed, 100.3 DPS, 33 STA, 22 Defense Rating, 21 Expertise Rating
Acquired from: Supremus, Black Temple
Personal thoughts: Much akin to the Mallet of the Tides, this weapon is good as a swap in later on for extended fights. The 21 Expertise Rating (5.04 Expertise) is a jump up from the Mallet of the Tides, and a recommended upgrade for Blood Elven, Dwarven, and Draenei Paladins, but for Humans, the racial trumps the additional stats here, so stay with the previous weapon.
Gauntlets of Enforcement: Plate Hands, 1,103 Armor, 70 STA, 32 Defense Rating, 21 Expertise Rating, 36 Block Value
Acquired from: Teron Gorefiend, Black Temple
Personal thoughts: Thanks to the Expertise, much like the Bracers of the Ancient Phalanx, these are arguably the best tanking gauntlets in the game. The Expertise rating on them gives 5.04 Expertise.
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Assuming you can get your hands on all four pieces of armor you can reach 20.16 Expertise or -5% to Parry and Dodge. This isn't counting the additional bonuses that can come from swapping in one of the weapons or from the Combat Expertise talent.
Final thoughts: Expertise is a sorely lacking talent right now, since most of the Expertise that is being added is replacing previously existing +weapon skill gear. Since Weapon Skill's primary purpose was the same as Expertise (lower dodge and parry chance) but also gave other additional effects, I believe Blizzard was reluctant to hand out too much of it, but now with it being changed into Expertise, I would not be surprised if we saw more of it on Plate in Sunwell Plateau (both the 5-man and the 25-man) and possibly even some of it on our Tiered Sets in WotLK.
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