Peer-to-peer-based video on demand (P2P-VoD) streaming systems have been widely used in delivering multimedia content. However, There are several problems existing in the P2P-VoD streaming systems, such as unstable video playing, low-utilization rate of video, and high server load, severely influencing viewers’ quality-of-experience (QoE). How to reasonably and efficiently schedule video chunks is important to handle the above-mentioned issues. In this paper, we propose a novel QoE-oriented chunk scheduling in a P2P-VoD streaming system, containing a request queue-based load balancing (RQLB) strategy and an elimination index-based cache replacement (EICR) strategy. In the proposed RQLB strategy, we first define the priority of the chunk requests, making the high-priority requests handled in time. Subsequently, we construct the utilization function of peer, so that the relatively low-priority requests will be transferred to the candidate neighbors with low utilization and high reliability. In the designed EICR strategy, we first calculate the elimination index for determining the candidate video. Considering the fact that chunks in a video may have different popularities, we then select the chunk with the lowest cache value for replacement. Moreover, we implement a real P2P-VoD system based on the proposed chunk scheduling scheme, giving the detailed design process of the network elements. Experimental results show that our proposed strategies can effectively solve chunk scheduling problem in the P2P-VoD streaming system, guaranteeing viewers’ QoE.