The use of HVDC systems is increasing in number due to technological innovations, increasing power capacity and increasing customer demand. The characteristics of insulation systems under composite DC and LI voltage must be examined and clarified. In this study, firstly, experimental circuits were designed to generate and measure composite DC and LI high voltage using a simulation program. The coupling elements used were chosen according to simulation results. Afterward, experimental circuits were established in the laboratory according to the simulation results of the designed experimental circuit. Then, breakdown voltages under composite DC and LI voltage for less uniform and non-uniform electric fields were measured with four different electrode systems for positive and negative DC voltage pre-stresses with different amplitudes. The 50% breakdown voltage was calculated using the least-squares method. Finally, 3D models were created for the electrode systems used in the experiments using the finite element method. The efficiency factors of electrode systems calculated with the FEM results were correlated with the experimental breakdown voltage results. Thus, the breakdown behavior of air under bipolar and unipolar composite voltages (CV) was investigated. In conclusion, the experimental results showed that very fast polarity change in bipolar CV causes higher electrical stress compared to unipolar CV.