This study focuses on the degradation behaviour of metallised film capacitors, which are the essential components for the stability of converter valves in flexible ultra‐high voltage direct current (HVDC) transmission systems. Through systematic experimentation, we investigated the failure mechanisms of MFCs under HVDC fields with superimposed harmonics, considering both equipment and material perspectives. The experiments subjected capacitors to 500 h of ageing under two conditions: a DC/AC‐superimposed field with a constant DC component of 290 kV/mm and an AC ripple rate varying from 12% to 28%, and a control group aged solely under a DC field. Our findings indicate that capacitors aged under the DC/AC‐superimposed field exhibited shorter lifespans and more significant capacitance loss than those aged under only the DC field. This difference in performance is primarily attributed to the distinct electrode loss behaviours observed under each ageing condition, which are key factors in the capacitors' capacitance decay. Moreover, the biaxially oriented polypropylene films in the DC‐aged samples showed more severe deterioration, characterised by more noticeable molecular chain scission and reduced breakdown strength, compared to those aged under the DC/AC superimposed field. This difference is partly due to the moderate temperature increase caused by harmonics, which benefits the aggregation structure, and partly to the reduced molecular structure damage from the AC field.