Благодаря http://blog.hasmanythrough.com/2007/10/30/self-referential-has-many-through, я смог собрать что-то, что работает.
в приложении / models / user.rb
has_many :mentee_relationships, :class_name => 'MentoringRelationship', :foreign_key => :mentor_id
has_many :mentees, :through => :mentee_relationships, :source => :mentee, :foreign_key => :mentor_id
has_many :mentor_relationships, :class_name => 'MentoringRelationship', :foreign_key => :mentee_id
has_one :mentor, :through => :mentor_relationships, :source => :mentor, :foreign_key => :mentee_id
в приложении / models / mentoring_relationship.rb
belongs_to :mentee, :class_name => "User"
belongs_to :mentor, :class_name => "User"