Separators with high security, reliability, and rate capacity are in urgent need for the advancement of high power lithium ion batteries. The currently used porous polyolefin membranes are critically hindered by their low thermal stability and poor electrolyte wettability, which further lead to low rate capacity. Here we present a novel promising porous polybenzimidazole (PBI) membrane with super high thermal stability and electrolyte wettability. The rigid structure and functional groups in the PBI chain enable membranes to be stable at temperature as high as 400 °C, and the unique flame resistance of PBI could ensure the high security of a battery as well. In particular, the prepared membrane owns 328% electrolyte uptake, which is more than two times higher than commercial Celgard 2325 separator. The unique combination of high thermal stability, high flame resistance and super high electrolyte wettability enable the PBI porous membranes to be highly promising for high power lithium battery.