In the emerging field of nanoscience, tubular structures have been attracting remarkable interest due to their well-defined geometry, high specific area, and exceptional physical and chemical properties. Among them, oriented ZnO tubular arrays are regarded as promising candidates for various applications such as optoelectronics, solar cells, sensors, field emission, piezoelectrics, and catalysis. Although template-directed and selective dissolution synthesizing strategies are commonly used to prepare ZnO nanotubes, repeatability and large scale preparation are still challenging. In this study, ZnO nanotube arrays were controllably prepared by tuning the hydrothermal parameters, without the use of any additives. The mechanism underlying the self-conversion of ZnO nanorods to nanotubes was comprehensively studied based on the surface energy theory. It has been proved that the metastable top surface of the ZnO nanorods dissolves preferentially to reach a stable state during the hydrothermal growth. The specific surface energy of different crystal faces of ZnO nanorods was calculated using molecular dynamics simulation. The top surface of the ZnO nanorod, the Zn-terminated [0001] face, demonstrated much higher surface free energy than did the lateral faces, which indicated that the self-dissolution of top face (002) is energetically favorable. The self-conversion behavior of ZnO nanorod arrays with different diameters was specifically investigated by adjusting the initial precursor concentration, density of the crystal seed layers, and growth time. The dissolution-crystallization equilibrium concentration, determined by crystal surface energy, was found to be a key factor for the formation of the tubular structure. Notably, the critical equilibrium conditions for the self-conversion of ZnO nanorods to nanotubes, including zinc ion concentration and pH, have been identified by studying parameters corresponding to the dissolution-crystallization equilibrium for the metastable top surface of the ZnO nanorods. The preparation of the ZnO nanotube arrays was successfully accelerated and simplified via two-step procedure: (1) preparation of ZnO nanorod arrays and (2) self-conversion of ZnO nanorods to nanotubes. The preparation method based on the self-conversion mechanism from rods to tubes for polar oxides is simpler and more easily controllable as compared to the reported methods involving variety of additives. Because of the advantages of adaptability to a wide range of substrates, excellent conducting properties, and filling ability, the prepared ZnO nanotube array films were used in encapsulating phase-change materials. The encapsulated phase-change material exhibited excellent heat storage/release properties and heat conductivities. This indicates the potential application of precision devices for temperature control.