Creating a UNIQUE constraint from a JSON object
First and foremost: I agree with both the comments of @a_horse_with_no_name and @dezso: you should normalize your data. JSON is not for that. 

However, if some  reason I cannot fathom really makes this an advantage, it is possible:

Create an expression based UNIQUE INDEX:

CREATE UNIQUE INDEX people_data_pos_idx ON peoples( (data-&gt;&gt;'pos') ) ;


If, at this point, you try to insert the following piece of data into your table (with an already existing ->>pos):

INSERT INTO peoples(data)
VALUES
    ('{"name": "Eve", "pos":"DBA", "age":34}') ;


You get this as a response:

ERROR: duplicate key value violates unique constraint "people_data_pos_idx"
SQL state: 23505
Detail: Key ((data -&gt;&gt; 'pos'::text))=(DBA) already exists.


NOTE: I've assumed that data.pos will always be a string. If you want to generalize, you can use ( (data-&gt;'pos') ) instead. You would index then a JSON(B) expression instead of a text. Check JSON Functions and Operators.