Anchoring nanostructured MoS2 on a conductive carbon substrate is an effective approach to produce flexible binder-free electrodes for energy storage applications. However, they are commonly fabricated through time-consuming hydrothermal reactions. Herein, MoS2 nanosheet arrays grown on a flexible carbon fiber cloth (CC) have been synthesized within 2 h by using a microwave-assisted method. These vertically aligned MoS2 nanosheets with expanded interlayer spacing of approximately 1 nm densely cover the support surface and form an interconnected network with significant void space. When employed as anodes for lithium-ion batteries, the microwave-synthesized binder-free MoS2/CC composites exhibit a high areal capacity of 2.5 mAh cm−2 at 0.15 mA cm−2, excellent cycle performance, and good rate capability.