In situ photopolymerized macroporous poly(glycidyl methacrylate-co-trimethylolpropane trimethacrylate) materials, which were prepared in a full factorial experimental synthesis design, were investigated as supports in solid phase chemiluminescence detection reactors. The reactors based on in situ polymerized supports showed higher light generation efficiency than packed bed reactors when evaluated in a flow system based on 1,1′-oxalyldiimidazolyl peroxyoxalate chemiluminescence detection of hydrogen peroxide, with 3-aminofluoranthene (3-AFA) as the immobilized light emitter. The results were correlated with the physical characteristics of the materials, and the efficiency was found to correlate with the amount of accessible reactive groups. A lower functionalization density was found to increase the peak area sensitivity for hydrogen peroxide in the flow system. This is explained by inner filtering. The peak height sensitivities were less influenced, indicating that the total system efficiency was limited by homogeneous reaction kinetics. The introduction of a spacer to mimic "pseudosolution" conditions of the bound 3-AFA moiety was found to decrease the light generation ability.