Flexible freestanding electrodes are highly desired to realize wearable/flexible batteries as required for the design and production of flexible electronic devices. Here, the excellent electrochemical performance and inherent flexibility of atomically thin 2D MoS2 along with the self-assembly properties of liquid crystalline graphene oxide (LCGO) dispersion are exploited to fabricate a porous anode for high-performance lithium ion batteries. Flexible, free-standing MoS2-reduced graphene oxide (MG) film with a 3D porous structure is fabricated via a facile spontaneous self-assembly process and subsequent freeze-drying. This is the first report of a one-pot self-assembly, gelation, and subsequent reduction of MoS2/LCGO composite to form a flexible, high performance electrode for charge storage. The gelation process occurs directly in the mixed dispersion of MoS2 and LCGO nanosheets at a low temperature (70 °C) and normal atmosphere (1 atm). The MG film with 75 wt% of MoS2 exhibits a high reversible capacity of 800 mAh g−1 at a current density of 100 mA g−1 . It also demonstrates excellent rate capability, and excellent cycling stability with no capacity drop over 500 charge/discharge cycles at a current density of 400 mA g−1 .