The understanding concerning structure formation during maleic anhydride plasma polymerization is focused based on growth kinetics study and chemical force titration through atomic force microscopy. Growth kinetics suggested that beads were formed initially and acted as intermediate for the random formation of needle-like and branched structures. The structures surface area followed a linear trend, except for the beads surface area that levels-off. Chemical force titration revealed that all the samples exhibited two pKa values, but the shifting of the values and the different trends indicated differences in the global chemistry of the films, associated to the presence of the structures.