Polymers synthesized with a star-shaped architecture can exhibit properties that differ from linear polymers. This has led several industries to use star polymers in their products. The utility of star polymers is currently restricted to high molecular weight applications because it is difficult to reproducibly isolate well controlled, low molecular weight star polymers. Consequently, little is known about the properties or behavior of star polymers in the low molecular weight regime. In this work, low molecular star polymers are reproducibly prepared using atom transfer radical polymerization. From simple homopolymers to more complex terpolymer compositions, stars with different cores, numbers of arms and arm lengths are studied. The potential of star polymers as photoresists is investigated to demonstrate the ability of stars in an application that requires extremely low (sub-10 kg/mol) molecular weights. Lithographic performance is comprehensively examined over a range of processing conditions using combinatorial techniques. This study reveals that the conformation of star polymers can result in smoother lithographic features, addressing a key challenge facing the photoresist community.