Natural cellulose fibres have been employed for packaging applications for a long time. Their use, however, has been hampered by their high hydrophilicity and their moisture sensitivity. It has, thus, been proposed to circumvent this problem through the hydrophobic modification of their surface thanks to the use of molecular grafting approaches.In this work, we describe the use of a novel solvent-free chemical pathway for molecular grafting that we have coined chromatogenic chemistry. It involves a reaction between a solid substrate and a reagent which is in a vapour-liquid equilibrium and diffuses within the solid substrate through a mechanism of adsorption/desorption akin to gas chromatography.Chromatogenic chemistry phenomenon has been studied and modelled through the extensive use of a new specific test, the Droplet Surface Migration Test. It involves the deposition upon a porous substrate of a small amount of reagent and in studying its subsequent migration and grafting. Whatman paper and various long chain acid chlorides were used for this modelling. The acid chloride carboxylic ends react with the external hydroxyl groups of cellulose fibres to give rise to the formation of long chain hydrophobic ester bonds. Upon immersion of the paper sheet in distilled water, a hydrophobic spot, extending well over the initial depot zone, could then be clearly visualized, allowing to follow conveniently the reagent migration and reaction. Grafting densities were performed by using the HPLC technique.The results obtained through the use of this test allowed a better understanding of chromatogenic chemistry phenomenon and an identification of the main parameters which affect the process: the nature of the reagent, the temperature, the reaction time, the nature of the substrate, etc. We have more particularly shown that the diffusion and grafting yields were maximal for a specific temperature which increases with the boiling point and therefore with the chain length of the reagents. We have proposed that this temperature should correspond to a compromise between the diffusion and reactivity properties of the reagent, its evaporation and its degradation by hydrolysis.