For in situ monitoring of fast changes of shear modulus and chemical conversion during UV radiation curing an ultrasonic (US) reflection method was combined with real-time near infrared (NIR) spectroscopy. The combined setup has been applied to study photopolymerization of different resins as acrylates, epoxy acrylates, acrylated polyurethanes and cationic epoxy resins in order to achieve a deeper understanding of the interdependence of reaction kinetics and changes of mechanical/rheological properties. The simultaneously recorded conversion-time and modulus-time curves allow differentiating between mass and diffusion controlled polymerization regime. Light curing and dark curing phases are indicated by two distinct regions in the conversion-time curves. By rescaling the curing time by chemical conversion modulus-conversion curves were constructed, which are described by combining a viscoelastic relaxation model with the conversion dependence of relaxation times. The NIR-US setup was used to study the influence of chemical composition and curing conditions on the polymer network formation. (C) 2012 Elsevier Ltd. All rights reserved.