The objective of this study was to investigate the behavior of highly functional acrylates, during isothermal ultraviolet (UV) curing. The materials included a pentafunctional acrylate and two acrylated hyperbranched polymers, one with a stiff polyester core and one with a more flexible polyether core. In particular, the influence of UV intensity and reactive blend composition on structural transitions, such as gelation and vitrification, and on the dynamics of internal stress was considered. Curing kinetics were studied with photo differential scanning calorimetry. The chemical conversion was analyzed using an autocatalytic model and a criterion for identifying vitrification directly from photocalorimetric experiments was proposed. It was observed that reactive blends containing HBPs had a higher conversion at vitrification, compared to the pure penta-functional acrylate. Strong intensity dependence of the maximum conversion rate and a weak intensity dependence of the ultimate conversion were observed. The latter was found to be controlled by the conversion at vitrification. The structural transitions and the modulus build-up during UV polymerization were determined by photorheology. A refined data processing algorithm was developed, that allows monitoring the shear modulus over 5 orders of magnitude within a short experimental time scale, with millisecond time resolution. Gelation – the liquid-solid transition – was found to be below 5 % conversion for all acrylates investigated. In contrast, the conversion at vitrification was strongly dependent on the actual monomer and increased with increasing UV intensity. The results of the photo DSC and the photorheology study were synthesized in the form of timeintensity- transformation diagrams. The dynamics of internal stress and cure shrinkage were studied using beambending and an interferometry-based method, respectively. The internal stress of the acrylated HBPs was largely reduced compared to the standard highly functional acrylate monomer. Moreover, in the case of one HBP with a polyester core and a reactive blend of the HBP with the standard highly functional acrylate, the stress reduction was obtained with a combined increase of Young's modulus, which was attributed to retarded modulus build-up and a higher final conversion. It was found that curing at a lower UV intensity led to earlier vitrification, hence earlier internal stress build-up, but limited maximum conversion thus limited final stress. Curing at a higher intensity led to later stress build-up but higher final stresses. Polymer microstructures were fabricated from the different acrylates in a photolithographic process and compared to SU-8, an epoxy frequently used for this kind of application. It was shown that the shape accuracy is linked to the processinduced internal stresses: the best result for thick and high aspect ratio microstructures – as used for example for microfluidic devices – was obtained for the acrylated HBP with a polyether core.