The penetration enhancement behaviors of a reactive material double-layered liner (RM-DLL) shaped charge against thick steel targets are investigated. The RM-DLL comprises an inner copper liner, coupled with an outer PTFE (polytetrafluoroethylene)/Al reactive material liner, fabricated via a cold pressing/sintering process. This RM-DLL shaped charge presents a novel defeat mechanism that incorporates the penetration capability of a precursor copper jet and the chemical energy release of a follow-thru reactive material penetrator. Experimental results showed that, compared with the single reactive liner shaped charge jet, a deeper penetration depth was produced by the reactive material-copper jet, whereas the penetration performance and reactive material mass entering the penetrated target strongly depended on the reactive liner thickness and standoff. To further illustrate the penetration enhancement mechanism, numerical simulations based on AUTODYN-2D code were conducted. Numerical results indicated that, with increasing reactive liner thickness, the initiation delay time of the reactive materials increased significantly, which caused the penetration depth and the follow-thru reactive material mass to increase for a given standoff. This new RM-DLL shaped charge configuration provides an extremely efficient method to enhance the penetration damage to various potential targets, such as armored fighting vehicles, naval vessels, and concrete targets.