Indexes can also be used to enforce uniqueness of a column's value, or the uniqueness of the combined values of more than one column.

CREATE UNIQUE INDEX name ON table (column [, ...]) [ NULLS [ NOT ] DISTINCT ];

Currently, only B-tree indexes can be declared unique.

When an index is declared unique, multiple table rows with equal indexed values are not allowed. By default, null values in a unique column are not considered equal, allowing multiple nulls in the column. The NULLS NOT DISTINCT option modifies this and causes the index to treat nulls as equal. A multicolumn unique index will only reject cases where all indexed columns are equal in multiple rows.

PostgreSQL automatically creates a unique index when a unique constraint or primary key is defined for a table. The index covers the columns that make up the primary key or unique constraint (a multicolumn index, if appropriate), and is the mechanism that enforces the constraint.