The shortage in energy has given rise to the development of biomass as advanced energy materials. As a by-product of microalgae biofuel, a large amount of residual broken microalgaes have an urgent requirement to be utilized by an environmentally friendly and economically feasible technology. In this paper, we reported that a hierarchically porous ZnMn2O4/biocarbon (ZMO/BC) microsphere fabricated via the residual broken microalgaes as templates, which can be applied as the electrode materials of lithium ion batteries. Based on the hierarchical porosity and the unique nanocapsules-like biocarbon structure formed in cycling, the ZMO/BC composites exhibited a superior electrochemical property. More attractively, the electrodes of such materials with Na-alginate as binder (also derived from algaes) exhibited the highest ever capacity, superior rate performance and the excellent long-term cycling stability. (C) 2016 Elsevier B.V. All rights reserved.