Topological modes in one- and two-dimensional systems have been proposed for numerous applications utilizing their exotic electronic responses. The 1D, zero-energy, topologically protected end modes can be realized in structures implementing the Su–Schrieffer–Heeger (SSH) model. While the edge modes in the SSH model are at exactly the mid-gap energy, other paradigmatic 1D models such as trimer and coupled dimer chains have non-zero energy boundary states. However, these structures have not been realized in an atomically tuneable system that would allow explicit control of the edge modes. Here, we demonstrate atomically controlled trimer and coupled dimer chains realized using chlorine vacancies in the c(2 × 2) adsorption layer on Cu(100). This system allows wide tuneability of the domain wall modes that we experimentally demonstrate using low-temperature scanning tunneling microscopy (STM).