Of course you can, in the sense that your RDBMS will let you do it. The answer to a question of whether or not you should do it is different, though: in most situations, values that have a meaning outside your database system should not be chosen to be a primary key.
If you know that the value is unique in the system that you are modeling, it is appropriate to add a unique index or a unique constraint to your table. However, your primary key should generally be some "meaningless" value, such as an auto-incremented number or a GUID.
The rationale for this is simple: data entry errors and infrequent changes to things that appear non-changeable do happen. They become much harder to fix on values which are used as primary keys.