To study the penetration and cratering effect of reactive material composite jets, a series of experiments are carried out for the shaped charge (SC) with different composite liners damaging steel targets. The inner layer of composite liners is metal and the outer one is a polytetrafluoroethylene/aluminum (PTFE/Al) reactive material. Copper (Cu), titanium (Ti) and Al inner liners are used in this paper. The reactive material liner is composed of 73.5 wt.% PTFE and 26.5 wt.% Al powder through mass-matched ratios. Reactive material composite liners are prepared through machining, cold pressing and a sintering process. The SC mainly consists of a case, a composite liner, high-energy explosive and an initiator. The steel target is steel 45#, with a thickness of 66 mm. A standoff of 1.0 CD (charge diameter) is selected to conduct the penetration experiments. The experimental results show that when the inner layer of the composite liner is composed of Ti and Al, the hole diameters on the steel target formed by the reactive material composite jet are significantly larger than that of the inner Cu liner. By introducing the initiation delay time (τ) and detonation-like reaction model of PTFE/Al reactive materials, an integrated numerical simulation algorithm of the penetration and detonation-like effects of reactive material composite jets is realized. Numerical simulations demonstrate that the initial penetration holes on the steel targets are enlarged under the detonation-like effects of PTFE/Al reactive materials, and the simulated perforation sizes are in good agreement with the experimental results.