Compositions of polylactide (PLA) and poly(3-hydroxybutyrate) (PHB) thermoplastic polyesters originated from the nature raw have been obtained by blending under shear deformations and electrospinning methods in the form of films and nanofibers as well as unwoven nanofibrous materials, respectively. The degrees of crystallinity calculated on the base of melting enthalpies and thermal transition temperatures for glassy state, cold crystallization, and melting point for individual biopolymers and ternary polymer blends PLA-PHB- poly(ethyleneglycol) (PEG) have been evaluated. It has been shown that the mechanical properties of compositions depend on the presence of plasticizers PEG with different molar masses in interval of 400-1000. The experiments on the action of mold fungi on the films have shown that PHB is a fully biodegradable polymer unlike PLA, whereas the biodegradability of the obtained composites is determined by their composition. The sorption activity of PLA-PHB nanofibers and unwoven nanofibrous PLA-PHB composites relative to water and oil has been studied and the possibility of their use as absorbents in wastewater treatment from petroleum products has been demonstrated.