This article proposes a novel parallel management mode based on decentralized autonomous organizations (DAOs) for enterprises by utilizing the artificial systems, computational experiments, parallel execution (ACP) approach, parallel intelligence theory, and blockchain technologies, to realize the distributed management of an enterprise. The artificial enterprise DAO (EnDAO) corresponding to the actual enterprise is constructed, and they constitute a parallel system via virtual–real interaction and parallel execution. Through the non-fungible token (NFT)-based incentive mechanism, metaverse-based virtual learning and training, as well as DAO-based distributed management and decision-making, the management and control of the actual enterprise as well as its employees can be carried out. By virtue of the virtual–real interactions of three types of employees, as well as the virtual–real feedback of three closed loops in the parallel systems, DAO-based parallel management for enterprises can realize descriptive intelligence, predictive intelligence, and prescriptive intelligence. On this basis, this article takes the recruitment-oriented key performance indicator (KPI) management of a startup technology enterprise as the case to introduce the operation processes and illustrate the superiorities of the proposed DAO-based enterprise parallel management mode.