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We study the structure of vapor-deposited glasses of five common organic semiconductors as a function of substrate temperature during deposition, using synchrotron X-ray scattering. For deposition at a substrate temperature of ∼0.8 T g (where T g is the glass transition temperature), we find a generic tendency towards “face-on” packing in glasses of anisotropic molecules. At higher substrate temperature however this generic behavior breaks down; glasses of rod-shaped molecules exhibit a more pronounced tendency for end-on packing. Our study provides guidelines to create face-on and end-on packing motifs in organic glasses, which can promote efficient charge transport in OLED and OFET devices respectively.more » « less