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The following is a non-exhaustive list of ways that unique items can be obtained. Unique items can always be traded.
World drops: Unique items, like items of any other rarity, can randomly drop from slain monsters and loot containers. A unique item’s drop level may differ from that of its base item. The actual drop levels of unique items are not known; however, there are examples of unique items that are known to only drop from very high level content, such as maps. Each unique item also has its own drop rate. These rates are not publicized by Grinding Gear Games, but certain unique items are clearly much more common than others.
Optional content: Optional game content is a prevalent source of unique items. Random unique item drops are often given to the player as reward for engaging with certain optional game content such as Heist, the Immortal Syndicate and the Lord’s Labyrinth just to name a few. They are sometimes indicated by a icon. Additionally, a number of drop-restricted unique items can only be acquired from optional game content and bosses.
Orb of Chance: Using an Orb of Chance on a normal item will very rarely upgrade it to a unique item of the same base type. For example, it is possible for a normal Gold Ring to be upgraded to Andvarius by using an Orb of Chance on it. Similarly, a Tainted Mythic Orb can also transform a corrupted item into a unique item with a risk of destroying it. These methods cannot be used to obtain drop-restricted unique items.
Vaal Orb: Certain jewels and equipment can only be created through one possible outcome of using a Vaal Orb on an item. For example, using a Vaal Orb on Tear of Purity may result in it transforming into Blood of Corruption.
Upgrading: Some unique items can be upgraded to a superior version. See blessed items and vials for more information.
Transforming: Ancient Orb and the Altar of Sacrifice in the Temple of Atzoatl can transform a unique item into another unique item. This cannot be used to obtain drop-restricted items.
Vendor recipes: Certain unique items can be created using vendor recipes. For most them, the vendor recipe is the only way to obtain it.
Divination cards: Sets of many divination cards can be turned in for unique items. Some like Thunderous Skies return specific unique items, whereas others like Jack in the Box return random ones. A few unique items like Maw of Mischief can only be acquired from specific divination card sets.
Event prizes: In the past, special unique items were given as prizes to players who placed in competitive events like races.