The parameters of combustion synthesis and shock-wave initiation of reactive W/PTFE/Al compacts are investigated. Preliminary thermodynamic calculations showed the possibility of combustion of the W/PTFE/Al system at high adiabatic temperatures (up to 2776 °C) and a large proportion of condensed combustion products. The effect of the Al content (5, 10, 20, and 30 wt%) in the W/PTFE/Al system on the ignition and development of exothermic reactions was determined. Ignition temperatures and combustion rates were measured in argon, air, and rarefied air. A correlation between the gas medium, rate, and temperature of combustion was found. The shock initiation in W/PTFE/Al compacts with different Al content was examined. The extent of reaction in all compacts was studied by X-ray diffraction. The compositions with 10 and 20 wt% Al showed the highest completeness of synthesis after combustion and shock-wave initiation.