We investigate here the strain-induced growth of Cu at 600 °C and its interactions with a thermally grown, 270 nm-thick SiO2 layer on the Si(111) substrate. Our results show clear evidence of triangular voids and formation of triangular islands on the surface via a void-filling mechanism upon Cu deposition, even on a 270 nm-thick dielectric. Different coordination states, oxidation numbers, and chemical compositions of the Cu-grown film are estimated from the core level X-ray photoelectron spectroscopy (XPS) measurements. We find evidence of different compound phases including an intermediate mixed-state of Cu–O–Si at the interface. Emergence of a mixed Cu–O–Si intermediate state is attributed to the new chemical states of Cu x+, O x , and Si x+ observed in the high-resolution XPS spectra. This intermediate state, which is supposed to be highly catalytic, is found in the sample with a concentration as high as ∼41%. Within the Cu–O–Si phase, the atomic percentages of Cu, O, and Si are ∼1, ∼86, and ∼13%, respectively. The electrical measurements carried out on the sample reveal different resistive channels across the film and an overall n-type semiconducting nature with a sheet resistance of the order of 106 Ω.