Scattering investigations of the structure and chain conformations, and the rheological properties of polyelectrolyte complexes (PECs) comprising model polyelectrolytes are presented. The use of charged polypeptides - (poly)-lysine and (poly)-glutamic acid with identical backbones allowed for facile tuning of the system parameters, including chain length, side-chain functionality, and chirality. Systematic studies using small-angle X-ray scattering (SAXS) of liquid PEC coacervates revealed a physical description of these materials as strongly screened semidilute polyelectrolyte solutions comprising oppositely charged chains. At the same time, solid PECs were found to be composed of hydrogen-bonding driven stiff ladder-like structures. While the coacervates behaved akin to semidilute polyelectrolyte solutions upon addition of salt, the solids were largely unaffected by it. Rheology measurements of PEC coacervates revealed a terminal relaxation regime, with an unusual plateauing of the storage modulus at low oscillation frequencies. The plateau may be ascribed to a combination of instrumental limitations and the long-range electrostatic interactions contributing to weak energy storage modes. Excellent superposition of the dynamic moduli was achieved by a time-salt superposition. The shift factors, however, varied more strongly than previously reported with added salt concentration.