Learning the optimal structure of a Bayesian network (BN) from observational data has received considerable research attention. In most structure learning methods based on scoring and searching, the discrete space of BNs is used, and the scale of the network grows exponentially with the number of nodes n, that is, O(n!2Cn2). Any existing scoring function in the BN space has multiple peaks. Thus, when using heuristic algorithms, local optimum problems may occur while searching in this space. As the search process involves only a small part of the space, the final learning result is not always ideal. In this study, the scoring and searching task is implemented in the complete node ordering space, and a novel neighbor operation is proposed for improving learning accuracy. This technique reduces the search space to O(n!) and facilitates optimized learning of a structure. Furthermore, techniques for efficiency optimization are proposed, which address the problems of high computational complexity and repetitive calculation of family scores.