We have investigated the influence of number of arms on chain interpenetration in the growth of star poly[2-(dimethylamino)ethyl methacrylate] (PDEM)/star poly(acrylic acid) (PAA) multilayers using a quartz crystal microbalance with dissipation (QCM-D). The oscillations in the changes of dissipation and frequency reflect the chain interpenetration and the variation of the mass of multilayer, respectively. The QCM-D results demonstrate that the growth of multilayers has two different mechanisms in terms of chain interpenetration. That is, the arm chains of star PDEM insert into a predeposited PAA layer to form a swollen multilayer, but the complex of star PAA with predeposited star PDEM is an "octopus-like" structure forming a dense multilayer. The transition between these two penetration modes is controlled by the number of arms in the star polyelectrolytes. As the number of arms of either PAA or PDEM increases, it becomes more difficult for star PDEM to penetrate into the PAA layer, but star PAA can more easily penetrate into the PDEM layer. According to atomic force microscopy and water contact angle measurements, all eight-bilayer multilayer surfaces have similar roughness values, and the surface wettability of the multilayers is dominated by the outermost PDEM layer.