The formation of polyelectrolyte complexes (PECs) prepared from oppositely charged linear polyelectrolytes (PELs) was studied by static light scattering at various salt concentrations. The PELs used were poly(allylamine hydro chlorid) (PAH) and the two polyanions poly(acrylic acid) (PAA) and poly(methacrylic acid) (PMAA). Physical characteristics such as radii of gyration and molecular weights as well as water content of the PECs were determined at various molar mixing ratios. In spite of the relatively small difference in chemical structure between PAA and PMAA, fairly large differences in the mentioned parameters were detected. Generally, PECs consisting of PMAA were larger and contained more water. Moreover, by using cryogenic transmission electron microscopy, transmission microscopy and atomic force microscopy, shape and structure of the prepared PECs were investigated both in solution and after drying. The PECs were found to be spherical in solution and the shape was retained after freeze-drying. PECs adsorbed on silica surfaces and dried in air at room-temperature still showed a three-dimensional structure. However, from the relatively low aspect ratios determined, the PECs were found to be significantly collapsed due to interactions with the silica surface during the adsorption and drying processes.