Three dimensionally ordered macroporous polybenzimidazole was successfully prepared as separator for Li metal deposition and dissolution. The effect of the newly developed separator on the Li metal deposition and dissolution reversibility was investigated. This separator can provide more uniform current distribution in Li vertical bar Li symmetrical cells, resulting in more uniform deposition of Li metal due to suppression of Li metal dendrites. The overpotential during Li metal deposition and dissolution was 50 mV at 10 mA cm(-2). The deposition and dissolution were stably repeated more than 3000 cycles. It can be said that the three dimensionally macroporous structure is highly useful in forming uniform Li metal.