The performance of poly(carbon monofluoride) (PMF) (synonym: graphite fluoride) (CFx)n, (1) as oxidizer in a fuel rich Mg based pyrolant (ξ(Mg)=0.45) is investigated. The radiance [W sr−1] under both static and dynamic conditions, the spectral radiant exitance [W cm−2 μm−1], the linear burn rate [mm s−1] and the mass consumption rate [g s−1 cm−2] have been determined. Calculations for enthalpy of anaerobic and aerobic combustion [kJ g−1] and for the equilibrium composition of the combustion products as well as combustion temperature are given. A mechanism for the reaction is discussed. The combustion product from Mg/(CFx)n surprisingly reveals the formation of single walled carbon nanotubes (SWCNT) and “carbon nano carpet rolls” (CNCR). For part V see Ref. .