From your code it becomes apparent that you use POCO. Having another key is unnecessary: you can add an index as suggested by juFo.
If you use Fluent API instead of attributing UserName property your column annotation should look like this:
this.Property(p => p.UserName)
.HasColumnAnnotation("Index", new IndexAnnotation(new[] {
new IndexAttribute("Index") { IsUnique = true }
}
));
This will create the following SQL script:
CREATE UNIQUE NONCLUSTERED INDEX [Index] ON [dbo].[Users]
(
[UserName] ASC
)
WITH (
PAD_INDEX = OFF,
STATISTICS_NORECOMPUTE = OFF,
SORT_IN_TEMPDB = OFF,
IGNORE_DUP_KEY = OFF,
DROP_EXISTING = OFF,
ONLINE = OFF,
ALLOW_ROW_LOCKS = ON,
ALLOW_PAGE_LOCKS = ON
) ON [PRIMARY]
If you attempt to insert multiple Users having the same UserName you'll get a DbUpdateException with the following message:
Cannot insert duplicate key row in object 'dbo.Users' with unique index 'Index'.
The duplicate key value is (...).
The statement has been terminated.
Again, column annotations are not available in Entity Framework prior to version 6.1.