We investigate the nature of the polyelectrolyte peak in salt-free solutions by molecular dynamics simulations using a minimal model of polyelectrolyte solutions that includes an explicit solvent and counterions and small angle scattering experiments. It is found that the polyelectrolyte peak progressively disappears as the strength of solvation for the charged species is increased and the scattering profiles start to resemble those of neutral polymer solutions. The disappearance of the polyelectrolyte peak coincides with the emergence of attractive interchain interactions over a wide range of length scales. These findings provide insights into the microscopic origin of the polyelectrolyte peak.