A facilitated anionic-surfactant-assisted method is developed to synthesize hierarchical microstructure Ni0.8Co0.1Mn0.1(OH)2 precursors. The anionic surfactant β-styrylphosphonic acid could directionally regulate the growth and the arrangement of the precursor nanosheets, where the primary nanosheets could maintain layered growth and ordered arrangement. The cathode material of the LiNi0.8Co0.1Mn0.1O2 synthesized from the above precursors exhibits best electrochemical performances and its capacity retention rates could reach 93 % (164.5 mAh g−1) after 100 cycles and 84.3 % (149.0 mAh g−1) after 300 cycles. Meanwhile, the detailed atomic arrangements on the crystal facets of cathodes are investigated both via first-principles calculations and transmission electron microscopy (TEM) analysis, and this research reveals that the crystal facet structures of cathode materials determine the electrochemical properties significantly.