Carbon nanotubes (CNTs) wrapped with layered double hydroxide (LDH-w-CNTs) were facilely obtained through in situ introduction of CNTs into the hydrothermal reaction system of LDH, with the goal of combining their unique physical and chemical characteristics to meet new advanced applications. Morphological observations indicated that LDH lamellae enwrapped the surface of CNTs and the wrapping degree was dependent on the functionalization of CNTs. Zeta-potential measurements showed that the interaction between the positive charge of LDH and the negative charge of CNTs was the main driving force of the wrapping process. Both hybrids led to a reduction in the peak heat release rate (PHRR) of polypropylene, indicating that they could confer better flame retardancy on polypropylene with respect to LDH and CNTs.