The earth abundant and environmentally friendly element iron (Fe) forms various functional materials of metallic iron, iron oxides, iron carbides, natural iron ore, and iron-based metallic-organic frameworks. The Fe-based materials have been intensively studied as oxygen carriers, catalysts, adsorbents, and additives in bioenergy production. This review was to provide a fundamental understanding of the syntheses and characteristics of various Fe-based materials for further enhancing their functionalities and facilitating their applications in various bioenergy conversion processes. The syntheses, characteristics, and applications of various iron-based materials for bioenergy conversion published in peer-reviewed articles were first reviewed. The challenges and perspectives of the wide applications of those functional materials in bioenergy conversion were then discussed. The functionalities, stability, and reactivity of Fe-based materials depend on their structures and redox phases. Furthermore, the phase and composition of iron compounds change in a process. More research is needed to analyze the complex phase and composition changes during their applications, and study the type of iron precursors, synthesizing conditions, and the use of promoters and supports to improve their performance in bioenergy conversion. More studies are also needed to develop multifunctional Fe-based materials to be used for multi-duties in a biorefinery and develop green processes to biologically, economically, and sustainably produce those functional materials at a large scale.