Recent advances in biopolymers, including functional biomaterials for the manufacture of personal protective garments (PPGs) or equipment (PPE) have dramatically improved their efficiency and performance. Good and acceptable permeation characteristics, mechanical strength and durability are common attributes of these materials simultaneously without compromise for their cost-effectiveness and manufacturability. The comprehensive characterization of these materials and specimens' three-dimensionality with the endeavor to obtain the highest resistance to highly toxic agents such as nuclear, chemical and biological warfare agents is the must fulfilling aim in today's global interest in continuous development in this area. Because energy absorption component seems to be important in considering quality the requirements related to the application of most protective materials (e.g. clothing), spectroscopy would seem to be the cornerstone to be considered for most analytical purposes to supplement the qualitative and quantitative assessment of polymeric materials. The major techniques worth mentioning include: scanning electron microscopy coupled to Xray dispersive spectroscopy (SEM/EDS), atomic force microscopy (AFM), scattering-type near-field optical microscopy, scanning tunneling microscopy (STM), attenuated total reflectance Fourier transform spectroscopy (ATR-FT-IR), infrared spectroscopic ellipsometry, nano-FTIR absorption spectroscopy, near-field optical microscopy, and infrared vibrational nano-spectrosocopy. This chapter will discuss the importance of a particularly important natural polymer (cellulose) containing acetyl groups to form modifiable biopolymers (e.g. cellulose acetate polymers), doped to yield multi-layered functional protective materials (MFPMs) or composites (MFPCs). The ultimate aim seeks to provide critical insights into understanding the enhancement of their permeation characteristics against exposure to toxic industrial chemicals, including chlorine which is currently being used as a chemical warfare agent of choice in the Syrian conflict. MFPMs or MFPCs are a group of materials made from a combination of fiber or polymers together with varying amounts of additives possessing tailored physical and mechanical properties. Many of these materials should not only be durable but also must provide cost-competi