The glass transition temperatures of poly(ethylacrylate), PEA, networks with several crosslink densities were determined by DSC and results were compared with those obtained from steady state fluorescence spectra of PEA networks with anthracene probes and labels. The latter measurements were performed as a function of temperature in the range 5 to 370K. PEA with phenylene labeled knots were studied in the range 240 to 370K. The fluorescence intensity decreases upon increasing temperature with several transition points in which the slope changes, both for probes and labels. One of the thermal transitions, set at about 320K, was compared to a liquid-liquid transition, while the glass transition was assumed to occur (at the microscopic level) in a broad range of temperatures which depends on the crosslink density and the position of the chromophore in the network. The first and the second temperature scans were not reproducible, similar to DSC thermograms, whereas the second and third were very similar.73111116