Spectral characteristics of ultraviolet and infrared rocket plume signatures are of great importance especially for detection, identification and tracking of approaching missiles. The objective was to find out significant differences between plume signatures of available real rocket motors based on double base and composite propellants. Therefore, the spectral emission ranges of 305–385 nm (UV) and 1.7–14 μm (MIR) were measured from the head‐on aspect. Additionally, reaction processes of applied propellant compositions were calculated by the ICT Thermodynamic‐Code and taken for the simulation of the theoretical spectra based on the ICT Band Modelling‐Code (BAM).