Spherical colloidal particles typically self-assemble into hexagonal lattices when adsorbed at liquid interfaces. More complex assembly structures, including particle chains and phases with square symmetry, were theoretically predicted almost two decades ago for spherical particles interacting via a soft repulsive shoulder. Here, we demonstrate that such complex assembly phases can be experimentally realized with spherical colloidal particles assembled at the air/water interface in the presence of molecular amphiphiles. We investigate the interfacial behavior of colloidal particles in the presence of different amphiphiles on a Langmuir trough. We transfer the structures formed at the interface onto a solid substrate while continuously compressing, which enables us to correlate the prevailing assembly phase as a function of the available interfacial area. We observe that block copolymers with similarities to the chemical nature of the colloidal particles, as well as the surface-active protein bovine serum albumin, direct the colloidal particles into complex assembly phases, including chains and square arrangements. The observed structures are reproduced by minimum energy calculations of hard core-soft shoulder particles with experimentally realistic interaction parameters. From the agreement between experiments and theory, we hypothesize that the presence of the amphiphiles manipulates the interaction potential of the colloidal particles. The assembly of spherical colloidal particles into complex assembly phases on solid substrates opens new possibilities for surface patterning by enriching the library of possible structures available for colloidal lithography.