This paper proposes a method to localize multiple partial discharge (PD) sources in air-insulated substation by using radio frequency (RF) antenna sensors combining with clustering algorithm, which solves the problem that multiple PD or interference sources are difficult to localize in air-insulated substation (AIS). Our research group made four omnidirectional RF antenna sensors, the detection frequency band was 250 MHz-3 GHz, the voltage standing wave ratio (VSWR) of the RF antenna in the detection frequency band was less than 2, which meets the detection requirements. The scenes of multiple PD sources in AIS were simulated in the laboratory, the time difference of arrival (TDOA) was collected through four RF antennas, and the clustering effects of K-means and Two Step algorithms were compared. Based on the normal distribution characteristics of TDOAs and the better Two Step algorithm, a <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$3\sigma $ </tex-math></inline-formula> -Two Step algorithm was proposed to process TDOAs and output the centers of TDOAs. Newton iterative algorithm was used to solve the localization equations. The results show that the average localization error of two PD sources was 0.21 m and that of three PD sources was 0.45 m. The PD localization tests were carried out in an actual AIS in China, the proposed method localized a corona discharge on a post insulator and a corona discharge on a disconnector. Through the verifications with an ultraviolet camera, it was obtained that the localization errors at each position were within the range of 0.6-2 m.