Niobium pentoxide reacts actively with concentrate NaOH solution under hydrothermal conditions at as low as 120 degrees C. The reaction ruptures the corner-sharing of NbO(7) decahedra and NbO(6) octahedra in the reactant Nb(2)O(5), yielding various niobates, and the structure and composition of the niobates depend on the reaction temperature and time. The morphological evolution of the solid products in the reaction at 180 degrees C is monitored via SEM: the fine Nb(2)O(5) powder aggregates first to irregular bars, and then niobate fibers with an aspect ratio of hundreds form. The fibers are microporous molecular sieve with a monoclinic lattice, Na(2)Nb(2)O(6).(2)/(3)H(2)O. The fibers are a metastable intermediate of this reaction, and they completely convert to the final product NaNbO(3) cubes in the prolonged reaction of 1 h. This study demonstrates that by carefully optimizing the reaction condition, we can selectively fabricate niobate structures of high purity, including the delicate microporous fibers, through a direct reaction between concentrated NaOH solution and Nb(2)O(5). This synthesis route is simple and suitable for the large-scale production of the fibers. The reaction first yields poorly crystallized niobates consisting of edge-sharing NbO(6) octahedra, and then the microporous fibers crystallize and grow by assembling NbO(6) octahedra or clusters of NbO(6) octahedra and NaO(6) units. Thus, the selection of the fibril or cubic product is achieved by control of reaction kinetics. Finally, niobates with different structures exhibit remarkable differences in light absorption and photoluminescence properties. Therefore, this study is of importance for developing new functional materials by the wet-chemistry process.