Differences in the content and the type of anions and cations in cigarette papers are often noted between what is added in the paper at the manufacturing stage, and what is found in the same paper taken from cigarettes after ageing. We also know that the amount and the type of burning agent in the cigarette paper have a strong influence on the carbon monoxide deliveries and on the ash appearance of the cigarettes. This phenomenon of anions and cations migration could therefore modify the results expected from the initial paper. The objective of this work is to study the migration of the cations and the anions from the tobacco to the cigarette paper and to evaluate its impact on the CO yields in particular and on the ash appearance of the cigarettes. As cigarette paper generally contains potassium and/or sodium salts, we initially studied the migration kinetics of potassium and sodium cations. Analyses were carried out by flame spectrophotometer. Paper without burning agent and papers with various contents and various types of burning agent were used. The identification of the anions transferred from the tobacco to the cigarette paper was carried out by capillary electrophoresis analyses of papers taken from aged cigarettes. Finally, the impact of the anions and cations migrations on the CO yields and the ash appearance of the cigarettes is discussed and illustrated with several examples.