The present study characterizes the formability of thin polyelectrolyte coatings applied on pseudoelastic NiTi-alloys. Due to their impact on the formation of defects in applied coatings, phase transformation induced topographies emerging on NiTi-substrates were thoroughly characterized. Polyelectrolyte films were deposited on electropolished surfaces from polyallylamine hydrochloride (PAH) and polyacrylic acid (PAA) solutions, using the layer by layer technique. Furthermore, PAH/PAA polyelectrolyte films were modified by heat treatment and incorporation of exfoliated organophile phyllosilicates. Defect formation within the films in different environments was subsequently detected by means of an in-situ experimental approach, combining cyclic pseudoelastic deformation of the substrates with high resolution microscopy techniques. By correlating microstructural properties, local strains and topographies with the observed defect formation, defects were revealed to emerge predominantly within areas of cyclically recurring phase- or grain boundary induced topographies. Topography height differences were related to the pronounced strain anisotropy of the NiTi-alloy as well as geometric effects across phase boundaries. Caused by water absorption and interactions with salt ions, a distinct increase of ductility was observed, bringing about highest formability of the films when exposed to Hanks solution. Heat treatment induced covalent bonding resulted in a drastic reduction of the film formability. By contrast, incorporation of silicates increased the formability at such a magnitude that no detectable defects emerged under the pseudoelastic deformations applied in the present study.