The photoemission spectra of Cu 2p are one of the most studied. Its analysis is especially challenging because, among others, the peaks for Cu⁰ and Cu¹⁺ overlap, and Cu¹⁺ and Cu²⁺ coexist under many conditions. The chemical state determination of metallic copper and the initial oxidation mechanism of copper require state-of-the-art peak fitting analysis and background modeling. This work presents a detailed and quantitative analysis of the Cu 2p photoemission spectra for a metallic ultra-thin film and the initial oxidation stages. Additionally, annealed films at 200°C for up to 5 min were analyzed to assess the full oxidation of the copper oxides and assert the validity of the proposed peak-fitting procedures. For the initial oxidation, it was possible to accurately identify Cu¹⁺ and Cu²⁺ states and, alongside, quantify the corresponding O 1s species, resulting in compositions close to stoichiometric values. Using the active background, it was possible to achieve close reproduction of all the photoemission spectra; three coexisting copper species were resolved during the fitting procedure. An accurate peak-fitting analysis allowed for quantifying the relative proportion of Cu¹⁺ to Cu⁰ states despite their strong overlap.