In this paper we describe the use of combinatorial vapor deposition techniques for the optimization of blue organic light emitting diodes (OLEDs). In these devices the star shaped molecule 1 with a triphenylamine core and three fluorene side groups serves as hole transport and emitting layer. Compound 2 with a much lower lying HOMO and a larger bandgap is used as hole blocking layer. Using combinatorial vapor deposition 42 OLEDs with thickness gradients of both the hole transport and the hole blocking layer have been simultaneously prepared on one substrate. The physical characterization of the devices clearly shows that a hole blocking layer of the star shaped molecule 2 is necessary in order to obtain pure blue emission with CIE coordinates of x = 0.15 and y = 0.15. A thickness of only 5 nm of the blocking layer is sufficient, and with increasing layer thickness the brightness of the blue devices drops. The blue devices exhibit a brightness of 400 cd m–2 and a luminous efficiency of 2 cd A–1. The thickness variations of both the hole transport and the hole blocking layer have been made in one combinatorial evaporation experiment on a single substrate using a set of movable masks. This demonstrates how efficient combinatorial methods can be used for the development of OLEDs.