Studies have been carried out aimed at the development of structures and technology for making special multi-layer textile-polymeric systems of shielding electromagnetic field (EMF). The use of textiles as EMF shielding materials is commonly known, however the EMF attenuation obtained practically exclusively results from the reflection of EMF, while the materials used for this purpose as a rule, show poor EMF absorption abilities. The basic assumption for a new solution is the exploitation of the multiple internal reflection of incident EMF either in textile-polymeric coating materials containing fine-particle electromagnetic materials or in special textile structures. This paper presents the results of investigating the EMF shielding effectiveness of several selected and developed textile-polymeric materials in respect of both their practical applications (protective clothing elements, technical materials, masking elements, etc.) and the structure and content of components with various EMF reflection and absorption properties. The measurement method for independent determination of reflection and transmission coefficients with a wavequide applicator was used. The results obtained with the 2.5 GHz to 18 GHz frequency range show a low value of transmission coefficient (min. −35 dB) and accepted reflection attenuation from about −4 dB to −15 dB for higher frequencies.