We investigate the two-dimensional (2D) colloidal structures formed by oppositely charged polystyrene monolayers grown layer-by-layer, where the electrostatic forces are recruited to assist in the packing of the layers. Our results show a transition through several 2D-superlattices to more close-packed structures with increasing ionic strength. The observed geometrical packing constraints of the 2D-superlattice structures agree well with the estimated Debye screening length of the electric double layer. By timing interaction forces between charged colloids, electrostatic interactions could enhance the template-directed self-assembly process to achieve more complex and diverse structures.