Here, atomistic molecular dynamics simulations are used to address the effect of different chemistry on the morphology, size, and shape characteristics of star polymers. The role of chemical details and features such as packing or flexibility on the structural properties of star‐like polymer melts is probed. Two types of symmetric unentangled homopolymer stars, the first consisting of atactic polystyrene (PS) and the second one of poly(ethylene oxide) (PEO) are studied. The star functionality f (i.e., the number of arms) is varied from f = 1 (linear chains) up to f = 32 and the shape and size characteristics are reported as a function of this main variable. The results from the monodisperse star‐like polymers are confronted with the theoretical predictions and with previously published simulations studies employing generic bead‐spring coarse‐grained models, with the aim to fill the gap between the systems studied experimentally and computationally.