Raising health and environmental concerns over the nanoparticles synthesized from hazardous chemicals have urged researchers to focus on safer, environmentally friendlier and cheaper alternatives as well as prompted the development of green synthesis. Apart from many advantages, green synthesis is often not selective enough (among other issues) to create shape-specific nanoparticle structures. Herein, we have used a biopolymer conjugate and Pd and Pt precursors to prepare sustainable bimetallic nanoparticles with various morphology types. The nanoparticles were synthesized by a novel green approach using a bio-conjugate of chitosan and polyhydroxybutyrate (Cs-PHB). The bio-conjugate plays the simultaneous roles of a reducing and a capping agent, which was confirmed by attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and energy dispersive X-ray spectrometry (EDS) analysis, proving the presence of a Cs-PHB layer on the surface of the prepared nanoparticles. The EDS profile also revealed the elemental structure of these nanoparticles and confirmed the formation of a Pd/Pt alloy. TEM morphological analysis showed the formation of star-like, octahedron or decahedron Pd/Pt nanoparticles, depending on the synthesis conditions. The bimetallic Pd/Pt nanoparticles synthesized with various Pd/Pt molar ratios were successfully applied for the catalytic reduction of 4-nitrophenol to 4-aminophenol by borohydride. The calculated κc values (ratio of k_app to the concentration of the catalyst) revealed that the decahedron nanoparticles (size of 15 ± 4 nm), synthesized at the molar ratio of 2:1 (Pd/Pt), temperature of 130 °C, 10 g/L of Cs-PHB conjugate and time of 30 min, exhibited excellent catalytic activity compared to other bimetallic nanoparticles reported in the literature.