If there are two people mentioned in a single sentence, it is better to say more friendly. If there is only one person mentioned in a single sentence, it is better to say friendlier.
Examples:
Bob is more friendly than Mary.
Bob is friendlier than Mary.
Bob is friendlier.
The cat is more friendly than the dog.
The cat is friendlier than the dog.
The cat is friendlier.
If Bob is "more friendly," he has to be more friendly than someone else. For friendlier, it can stand on its own or be used to compare two people in the same sentence.
So, it depends on the situation that you use each one.