The knowledge of lattice thermal conductivity of materials under realistic conditions is vitally important since many modern technologies require either high or low thermal conductivity. Here, we propose a theoretical model for determining lattice thermal conductivity, which takes into account the effect of microstructure. It is based on ab initio description that includes the temperature dependence of the interatomic force constants and treats anharmonic lattice vibrations. We choose ScN as a model system, comparing the computational predictions to the experimental data by time-domain thermoreflectance. Our experimental results show a trend of reduction in lattice thermal conductivity with decreasing domain size predicted by the theoretical model. These results suggest a possibility to control thermal conductivity by microstructural tailoring and provide a predictive tool for the effect of the microstructure on the lattice thermal conductivity of materials based on ab initio calculations. DOI: 10.1103/PhysRevB.96.195417 Design of modern materials inevitably requires taking the thermal conductivity into account [1]. For thermoelectric materials a low thermal conductivity is crucial to avoid heat transfer across the legs and therefore loss in energy conversion efficiency [2]. In contrast, electronic components require packaging materials with high thermal conductivity to efficiently dissipate the generated heat [3]. Furthermore, the more complex the devices become, the higher is the demand to control the interplay between microstructure and thermal performance [4,5]. For hard protective wear-resistant coatings, in, e.g., cutting or milling applications, thermal properties are often barely considered when optimizing mechanical and tribological properties, despite the fact that the workpiece is typically subject to temperatures locally exceeding 1100• C in the contact spots [6][7][8]. The requirements for thermal conductivity are therefore high: the in-plane heat spread within the coating should be as high as possible to ensure uniform heating, while the cross-plane thermal conductivity should be as low as possible to minimize the heat load on the substrate [6][7][8].These examples underscore how important it is to understand and be able to tailor thermal conductivity in materials in a broad range of applications.Measurements of thermal conductivity are relatively standard for bulk materials but much more challenging for thin films and nanoscale materials, still being the topic of active method development [9,10]. There is therefore a substantial need to also develop theoretical methods for predicting or simulating the thermal conductivity of real materials. Recent advances in methodology allow us to predict the thermal * Present address: Department of Materials Science and Engineering, Rensselaer Polytechnic Institute, Troy, New York 12180, USA.† Corresponding author: per.eklund@liu.se conductivity from first principles. In the present paper, we combine state-of-the-art computational techniques with characteriz...