It is well-known that the high-performance polymeric dielectric films used for high-voltage DC capacitors should have outstanding capabilities in terms of electrical and mechanical properties in order to face harsh operating conditions. Many factors limit the ability of these thin films to face different and growing stresses according to modern electrical requirements. Microstructure properties, additives, impurities, defects formed during manufacturing as well as applied stress types significantly affect the performance of dielectric films and their operational lifetime. This paper presents a comprehensive review of the factors which affect the ageing, degradation and breakdown of metallised polypropylene (PP) capacitors films. The effects of microstructure, surface morphological properties, mechanical properties and defects on the reliability of biaxially oriented polypropylene films (BOPP) are studied. In addition, the phenomena affecting dielectric performance and ageing mechanisms which are induced by electrical, thermal and electrothermal stresses are discussed.