The structural properties of copper complexes with (2-hydroxyphenyl)di-p-tolylphosphane oxide (CuL12) and 3-(2-hydroxyphenyl)-3,4-dihydro-2H-benzo[f][1,5,3]dioxaphosphepine 3-oxide (CuL22) are studied in detail. The o-phosphorylated phenols demonstrate both bridging and chelating behaviour, and the main reaction product is a coordination polymer containing dimeric Cu2O8 fragments. The structural peculiarities of the o-phosphorylated phenols were revealed by single-crystal X-ray diffraction. The copper complexes are studied by single-crystal and powder X-ray diffraction, and IR, Raman and X-ray photoelectron spectroscopy (XPS). The applicability of XPS spectroscopy to structural studies of coordination compounds with complex organic ligands is demonstrated with CuL12 and CuL22. The results of ab initio structure solution and Rietveld refinement of the CuL22 structure from powder data are augmented by PW-PBE-D calculations.