In Path of Exile, there’s only one way of getting great loot: get lucky. Loot is in integral part of the game and has its value, and we all want the best equipment possible for our characters. The only consistent way to get great endgame items is to craft them, which requires an enormous amount poe currency but is somewhat less RNG based, depending on how much you’re willing to invest.
If you’re hoping for an item to drop for you then you’re in for a rough ride. Items which are worth over 10 Exalted Orbs are of course extremely rare and while they seemingly keep dropping for other players more than they do for you there is a way to increase your chances of getting one. Chance Orbs have a miniscule possibility to turn a white item into a unique one, so using the orbs on particular whites can be a good strategy to maximize your farming time.
There are several high-value items and they include: Glorious Plate – Turns into Kaom’s Heart (value over 30 Exalted), Occultist’s Vestments – Turns into Shavronne’s Wrappings (value around 50 Ex unlinked, up to 80 if 6L); also chances in Infernal Mantle which is worth far less, Siege Axe – can be chanced for Soul Taker, valued at 50+ Exalted depending on roll, Spine Bow – Voltaxic Rift bow, valued at over 50 Ex, Note: approximate values are based on Standard league prices.
These are all some of the best poe items in game and highly valued by many skill tree builds, and rare enough to warrant their extreme prices. When farming Merciless Docks you should see at least 2-3 Siege Axes in a solo run, and Occultist’s Vestments are a bit more rare but still rather frequent. Glorious Plates and Spine Bows can drop in Docks or Lunaris as well but they drop more regularly once you get into 68+ map farming.
Other higher valued items still worth chancing are Hubris Circlets for Crown of Eyes, Nightmare Bascinets for Bringer of Rain & Devoto’s Devotion, Chain Belt for Auxium, Murder Mitts for Thunderfist, and Amethyst Ring for Ming’s Heart and Death Rush. All of these are worth between 10 and 30 Ex on average. There’s even more items you could try your luck with: Champion Kite Shield for Aegis Aurora, Sinner Tricorne for Alpha’s Howl, Gold Ring for Andvarius, Archon Kite Shield for Prism Guardian, Prophecy Wand for Void Battery, Slaughter Knife for Bino’s Kitchen Knife, Imperial Bow for Lioneye’s Glare and Sapphire Ring for Dream Fragments, though some of these may not be worth as much to make it worthwhile.