Each film preparation technique affects the physical properties of the resulting coating and thus defines its applicability in modern device construction. In this context solvent based spin coated and solvent-free physical vapor deposited molecular glass photoresist films are systematically investigated for their dissolution behavior, sensitivity, and overall lithographic performance. These investigations demonstrate that the solvent-free physical vapor deposition leads to a marked increase in sensitivity. This could be explained by the individual molecule by molecule deposition step producing a more homogeneous distribution of the multicomponent resist system, especially the photoacid generator. In addition, this assumption is supported by former published simulations focusing on aggregate formation within thin films. This work demonstrates that the lithographic sensitivity of multicomponent resist system is an intrinsic parameter to investigate molecular material distribution and indicates that the applied film preparation technique is crucial for the corresponding performance and applicability.