Hoop-shaped conjugated macrocycles (or carbon nanohoops) are eliciting significant interest from theoretical and synthetic scientists on account of their eminent physical and chemical properties. Herein, carbon nanohoops firstly fabricated by CH4 plasma treatment serve as toughening and lubricant agents in TiN porous films. The formation mechanism of carbon nanohoops is explained through a tandem Suzuki coupling/macrocyclization sequence of the charged multiple hydrocarbon molecules. The essential features of carbon nanohoops ensure that the TiN porous films with carbon nanohoops successfully possess flexible, hard, lubricant and antiwear effects. (C) 2016 Elsevier B.V. All rights reserved.