The cocoa roasting process at different temperatures (at 125 and 135 degrees C for 3 min, plus 44 and 52 min, respectively, heating-up times) was evaluated by measuring the initial and final free amino acids distribution, flavor index, formol number, browning measurement, and alkylpyrazines content in 15 cocoa bean samples of different origins. These samples were also analyzed in manufactured cocoa powder. The effect of alkalinization of cocoa was studied. Results indicated that the final concentration and ratio of tetramethylpyrazine/trimethylpyrazine (TMP/TrMP) increased rapidly at higher roasting temperatures. The samples roasted with alkalies (pH between 7.20 and 7.92), such as sodium carbonate, or potassium plus air injected in the roaster during thermal treatment, exhibited a greater degree of brown color formation, but the amount of alkylpyrazines generated was adversely affected. The analysis of alpha-free amino acids at the end of the roasting process demonstrated the importance of the thermal treatment conditions and the pH values on nibs (cocoa bean cotyledons), liquor, or cocoa. Higher pH values led to a lower concentration of aroma and a higher presence of brown compounds.