This paper analyzes the performance of single-shot digital holographic microscopy for rapid characterization of static step-index structures in transparent polymer materials and for online monitoring of the photoinduced polymerization dynamics. The experiments are performed with a modified Mach-Zehnder transmission digital holographic microscope of high stability (phase accuracy of 0.69°) and of high magnification (of ≈90×). Use of near-infrared illumination allows both nondestructive examination of the manufactured samples and monitoring of optically induced processes in a photosensitive material concurrently with its excitation. The accuracy of the method for a precise sample's topography evaluation is studied on an example of microchannel sets fabricated via two-photon polymerization and is supported by reference measurements with an atomic force microscope. The applicability of the approach for dynamic measurements is proved via online monitoring of the refractive index evolution in a photoresin layer illuminated with a focused laser beam at 405 nm. High correlation between the experimental results and a kinetics model for the photopolymerization process is achieved.