Polyelectrolyte complexes are omnipresent both in nature and in the technological world, including nucleotide condensates, biological marine adhesives, food stabilizers, encapsulants, and carriers for gene therapy. However, the true phase behavior of complexes, resulting from associative phase separation of oppositely charged polyelectrolytes, remains poorly understood. Here, we rely on complementary experimental and simulation approaches to create a complete quantitative description of the phase behavior of polyelectrolyte complexes that represents a significant advance in our understanding of the underlying physics of polyelectrolyte complexation. Experiments employing multiple approaches with model polyelectrolytes oppositely charged polypeptides poly(L-lysine) and poly(D,Lglutamic acid) of matched chain lengths led to phase diagrams with compositions of the complex and the supernatant that were in excellent agreement with simulation results. Contrary to the widely accepted theory for complexation, we found preferential partitioning of salt ions into the supernatant phase. Additionally, the salt partitioning into the supernatant phase was found to initially increase and then decrease on increasing the salt concentrations, manifesting as a distinct minimum in the salt partition coefficients. These trends were shown by simulations to be strongly influenced by the excluded volume interactions in the complex phase, which were not accounted for in their entirety in earlier theories. We believe the comprehensive data we present will be conducive to the development of an accurate physical theory for polyelectrolyte complexation with predictive capabilities.