Photopolymerization by four-beam interference lithography on a preheated SZ2080 sample was explored at different initial temperatures of the sample: 20 °C, 50 °C, 75 °C, 100 °C, 125 °C, and 150 °C, and at exposure times ranging from 0.5 s to 5 s. The average laser power selected was ∼100 mW for the 300 ps duration pulses at a 1 kHz repetition rate. The experimental results demonstrate that the higher initial temperature of the sample positively influences the crosslinking of the patterns. These findings will improve polymerization protocols for multi-beam interference lithography.