This article introduces asymmetric cyanine dyes employed as visible-light photoinitiators of vinyl monomer polymerization and as fluorescence probes monitoring the progress of polymerization. A degree of polymer cure from the measurement of the changes in the probe emission intensity and position shifts during the thermally initiated polymerization of monoacrylate was obtained. A distinct increase in the intensity of the probe fluorescence was observed during polymerization when the degree of monomer conversion was gradually increasing. This effect was accompanied by a blue-shift of the probe emission maxima. The second part of this work is focused on the possibility of an application of the tested dyes, in combination with borate anions, as photoinitiating systems. The kinetics of polymerization of trimethylolpropane triacrylate, with cyanine borates as photoinitiators, was studied by a microcalorimetric method. Asymmetric cyanine borates were found to be effective photoinitiators, and both the initiator and coinitiator concentration as well as the light intensity strongly affected the progress of photopolymerization, leading, for example, to an increase in the polymerization rate. (c) 2005 Wiley Periodicals, Inc.