We investigate the thermodynamic constraints on the pivotal task of entanglement generation using out-of-equilibrium states through a model-independent framework with minimal assumptions. We establish a necessary and sufficient condition for a thermal process to generate bipartite qubit entanglement, starting from an initially separable state. Consequently, we identify the set of system states that cannot be entangled, when no external work is invested. In the regime of infinite temperature, we analytically construct this set; while for finite temperature, we provide a simple criterion to verify whether any given initial state is or is not entangleable. Furthermore, we provide an explicit construction of the future thermal cone of entanglement—the set of entangled states that a given separable state can thermodynamically evolve to. We offer a detailed discussion on the properties of this cone, focusing on the interplay between entanglement and its volumetric properties. We conclude with several key remarks on the generation of entanglement beyond two-qubit systems, and discuss its dynamics in the presence of dissipation. Published by the American Physical Society 2024