Reduction of phonon mediated thermal transport properties, i.e., lattice thermal conductivity (κL), of semiconductors can strongly affect the performance of thermoelectrics and optoelectronics. Although extrinsic routes to reduce κL have been achieved through selective scattering of phonons via doping, alloying, and hierarchical nano-structuring, semiconductors with intrinsically low κL have recently gained widespread attention due to their ability to decouple electronic and phonon transports. While innate low κL in crystalline semiconductors is a desired requirement to achieve high performance thermoelectrics, the solar upconversion efficiency of photovoltaics based on metal halide perovskites (MHPs) have been shown to increase due to their ultralow κL through the hot-phonon bottleneck effect. Therefore, understanding the microscopic mechanisms underlying ultralow κL in crystalline semiconductors is extremely important. Several structural factors that are intrinsic to a material have been shown to strongly influence the reduction of κL. Among them, the presence of rattling atoms, lone-pair electrons, and large lattice anharmonicity have been widely studied. Here, we bring out yet another largely unexplored intrinsic characteristic of materials related to the filled antibonding valence states (AVS) near the Fermi level, which are shown to induce low κL in crystalline compounds. We focus our review on an emerging class of compounds–metal halide semiconductors including MHPs and investigate the interplay between structures, chemical bonding and κL, carefully curating from literature a list of 33 compounds having different structure dimensionality with known κL. We established a universal connection between the elastic moduli, speeds of sound, and κL with the presence of AVS just below the Fermi level. We found that large peak in the AVS correlates positively with lower values of elastic moduli, speeds of sound, and κL, providing antibonding states based design criteria of low-κL compounds. Furthermore, we discuss different synthesis strategies, which are crucial for experimental realization of ultralow κL through structure manipulation. Additionally, we outline how chemical bonding data can be utilized in machine learning models for predictive modeling of κL. We hope that our approach of understanding low-κL through the viewpoint of chemical bonding theory would encourage exploration of phonon transport properties in other families of materials having filled AVS that can provide further insights on the structure-bonding-property relationships aiding novel materials design approaches.