Objectives. The present study was carried out to create composites and fibers using polyurethane (PU) with hydroxyapatite (HA) that could be used for dental applications. Methods. Composites with varying HA concentration were prepared by solution casting technique. Similarly, PU-HA fibers with varying PU hard and soft segments and fixed HA concentration were also prepared. Various characterization techniques, such as, X-ray diffractometry, differential scanning calorimetry, scanning electron microscopy and Fourier transform infrared spectroscopy in conjunction with photo-acoustic sampling cell were employed to study the composites and fibers for changes in their physicochemical propertiesbefore and after immersion in artificial saliva at 37°C for up to 5 days. Results. The results indicated formation of amorphous apatite layers with maximum amorphicity in composites containing highest amount of HA with 5 days of immersion in artificial saliva. Similarly, fibers with more PU hard segment resulted in better transformation of crystalline HA to its amorphous state with increasing immersion time thus confirming the bioactive nature of the HA-PU fibers. Significance. Concentrations of HA and PU hard segment along with the duration of immersion in artificial saliva are two major factors involved in the modification of solid-state properties of HA. The amorphous apatite layer on the surface is known to have tendency to bind with living tissues and hence the use of optimum amount of HA and PU hard segment in composites and fibers, respectively could help in the development of novel dental filling material. © 2014 Academy of Dental Materials.