Polymers are gradually replacing conventional materials in various sectors of the economy because of their low cost and broad functionality. However, the high stability of polymers under most environmental conditions can lead to their accumulation in the form of waste. Polyhydroxybutyrate (PHB) is an alternative because of its biodegradability, but it is usually expensive and brittle. These aspects can be improved through the formation of blends, such as with polypropylene (PP). The objective of this study was to investigate the possibility of using titanium dioxide (TiO2) nanoparticles as a prodegradant agent in the PP–PHB–TiO2 system through the evaluation of the effects of these nanoparticles under UV light on the structure and properties of the materials. Samples were produced through extrusion and injection molding and were characterized by their mechanical and thermal properties and structural analyses. The results show that the TiO2 nanoparticles were able to act as a prodegradant agent for the PP–PHB blend; they also successfully improved some of the mechanical and dynamic mechanical properties of the blend. However, a TiO2 nanoparticle content higher than 7.5 wt % was not able to extend the photodegradation process further, possibly as a consequence of the agglomeration of nanoparticles during the processing of these more concentrated blends. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46636.