After the Cold War, relations between the PRC and the Association for South East Asian Nations (ASEAN) have improved, and the PRC has been in harmony with ASEAN in ASEAN-based regional organizations and multilateral dialogues. Nonetheless, on some political issues, both sides have not been able to reach consensus. This denotes the co-existence of positive and negative patterns of behavior in PRC-ASEAN political interactions. By means of the latest development of neorealism, this essay attempts to study the formation and development of PRC-ASEAN political cooperation mechanisms in the aftermath of the Cold War. Changes in the regional system and the impact of the PRC's and ASEAN's internal factors (including their perceptions of security threats) are the major independent variables in this essay. Both because the PRC and ASEAN have salient disagreement on the South China Sea dispute and because the internal factors of their own limit the development of PRC-ASEAN cooperation in political security, the current focal point of PRC-ASEAN political cooperation is confidence and security building. In the foreseeable future, international influences will make both the PRC and ASEAN try to avoid mutual conflict, but there may not be major breakthroughs in PRC-ASEAN political cooperation on account of their respective internal factors such as the insistence on national territorial sovereignty and the perceptions of the security environments.