Natural molybdenite has the advantages of low cost and high lithium storage capacity, which can be directly used as an anode material of lithium-ion batteries. In this paper, expanded molybdenite/carbon (EM/C) composites were constructed via expanding molybdenite and surface modification with dopamine. The worm-like structure of expanded molybdenite (EM) has a high specific surface area that is conducive to electrolyte infiltration and diffusion of lithium ions. The amorphous carbon layer effectively increases its electrical conductivity and provides a buffer space for volume enlargement during MoS2 cycle. The EM/C composites have a long cycle life and a high capacity, with a capacity of 1 213 mA·h/g at 100 mA/g after 200 cycles and a reversible capacity of 623 mA·h/g even at 1 A/g. The strategy of EM/C composite material constructed from molybdenite fine powder has a specific guiding significance to achieve the superior electrochemical performance of lithium-ion battery.