The current study presents for the first time how recovered carbon black (rCB) obtained directly from the industrial-scale end-of-life tires (ELTs) pyrolysis sector is applied as a precursor for activated carbons (ACs) with application in CO2 capture. The rCB shows better physical characteristics, including density and carbon structure, as well as chemical properties, such as a consistent composition and low impurity concentration, in comparison to the pyrolytic char. Potassium hydroxide and air in combination with heat treatment (500–900 °C) were applied as agents for the conventional chemical and physical activation of the material. The ACs were tested for their potential to capture CO2. Ultimate and proximate analysis, Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS), Raman spectroscopy, thermogravimetric analysis (TGA), and N2/CO2 gas adsorption/desorption isotherms were used as material characterization methods. Analysis revealed that KOH-activated carbon at 900 °C (AC-900K) exhibited the highest surface area and a pore volume that increased 6 and 3 times compared to pristine rCB. Moreover, the AC-900K possessed a well-developed dual porosity, corresponding to the 22% and 78% of micropore and mesopore volume, respectively. At 0 °C and 25 °C, AC-900K also showed a CO2 adsorption capacity equal to 30.90 cm3/g and 20.53 cm3/g at 1 bar, along with stable cyclic regeneration after 10 cycles. The high dependence of CO2 uptake on the micropore volume at width below 0.7–0.8 nm was identified. The selectivity towards CO2 in relation to N2 reached high values of 350.91 (CO2/N2 binary mixture) and 59.70 (15% CO2/85% N2).