Bismuth ferrite (BiFeO3) is a perovskite material well known for its multifunctional properties and related applications. The recent research on this material includes the synthesis of hollow-structured BiFeO3 using various methods and exploring their applications in photocatalysis and sensing. Here, we introduce a facile method for the synthesis of BiFeO3 hollow tubes using the sol-gel method, where kapok fiber collected from Ceiba pentandra is used as a biotemplate for the first time. In the procedure, the annealing path was modified by introducing intermediate holding steps besides varying the final annealing temperature. The structural analysis was carried out using X-ray diffraction (XRD) and Raman analysis, whereas the formation of hollow tube morphology was confirmed with the help of FESEM analysis. The complete decomposition of the kapok fiber template during the annealing process was confirmed with the help of Fourier transform infrared spectroscopy. The XRD analysis indicated that monitoring both the annealing pathway and the final annealing temperature is pivotal in attaining the formation of phase pure BiFeO3. The proposed method eliminates the requirement for additional procedures for extracting the synthesized hollow tubes from the parent template, in addition to providing a less expensive strategy for the synthesis of BiFeO3 hollow tubes.