Anionic collagen:P(VDF/TrFE) (75/25) membrane composites were prepared by mixing anionic collagen and P(VDF/TrFE) in aqueous concentrated acetic acid:dimethylsulfoxide solutions and characterized by infrared, electron scanning microscopy, thermal analysis and dielectric properties, The results show that under the appropriate conditions anionic collagen:P(VDF/TrFE) composites, with ratios in the range from 4:1 to 1:4 may be conveniently prepared in the form of membranes, without the loss of tropocollagen secondary structure. As suggested by infrared spectroscopy and thermal analysis, mixing is accompanied by macromolecular interaction conditions anionic collagen and P(VDF/TrFE). Although preliminary, the determined pyroelectric coefficient for the 1:1 composite of 1.89 x 10(-4)Cm(-2)K(-1), is higher than those determined under the same conditions for native, anionic collagen and P(VDF/TrFE) and of respectively 0.37 x 10(-4)Cm(-2)K(-1), 1.16 x 10(-4)Cm(-2) K-1 and 17 x 10(-6) Cm-2K-1, but comparable to that for PZT (4.2 x 10(-4)Cm(-2)K(-1)) at the same temperature. This increase in pyroelectric coefficient for the 1:1 composite, in respect to anionic collagen membranes, may be a result of a anionic collagen: P(VDF/TrFE) interaction. A model based on hydrogen bonding formation between acidic and alcoholic hydroxyl groups of anionic collagen and the fluorine atoms of P(VDF/TrFE) is proposed.