Massive quantities of spent coffee grounds (SCGs) are generated by users around the world. Different processes have been proposed for SCG valorization, including pyrolytic processes to achieve carbonaceous materials. Here, we report the preparation of activated carbons through pyrolytic processes carried out under different experimental conditions and in the presence of various porosity activators. Textural and chemical characterization of the obtained carbons have been achieved through Brunauer–Emmett–Teller (BET), ESEM, 13C solid state NMR, XPS, XRD, thermogravimetric and spectroscopic determinations. The aim of the paper is to relate these data to the preparation method, evaluating the correlation between the spectroscopic data and the physical and textural properties, also in comparison with the corresponding data obtained for three commercial activated carbons used in industrial adsorption processes. Some correlations have been observed between the Raman and XPS data.