Organic polymer surfaces are metallized in two general ways: (i) thin film metallization in which metals are deposited by vapor deposition, sputtering, etc. and (ii) relatively thick metal coatings are deposited by means of electroless deposition followed by electrolytic deposition. In the present review paper, various applicable mechanisms—mechanical or interlocking, weak boundary layer, chemical, and electrostatic—of adhesion, relevant properties of metals and polymers, and techniques of controlling adhesion in metallized polymers are discussed, but the thin metallization of polymers has been emphasized. Evidence and mechanisms for the charge transfer across the metal–polymer interface are reviewed and the electrostatic component of adhesion is discussed. Apparently, there is a linear relationship between the charge transferred across the metal–polymer interface and the work‐function difference between the metal and the polymer. It is concluded that the electrostatic component of adhesion may have some ...