Two polychromophoric dansyl hyperbranched fluorescent probes (HBPs) have been used as fluorescent sensors to follow photopolymerization reactions of acrylic monomers through fluorescence monitoring. Simultaneously, photo-DSC measurements were conducted. The combined data obtained by both techniques allowed to measure precise and adequately the kinetics of the systems. Differences are found depending on the composition of the formulation, but no depending on the probe inserted in the systems. The behavior and sensitivity of the functional HBP's have been compared with their low molecular weight monochromophoric reference compounds. Hyperbranched polychromophoric probes showed the same sensitivity towards the process than the monochromophoric probes, confirming the high sensitivity of the hyperbranched probes. Also, the data obtained by fluorescence allow distinguishing the different steps involved in the mechanism of a radical crosslinking polymerization, which could not be observed only with calorimetric measurements. The advantages of the functional HBP fluorescent probes towards their low molecular weight homologues are discussed. (C) 2015 Elsevier B.V. All rights reserved.