Formation of polymeric pillars by using laser interference lithography is compared for nanosecond and picosecond laser pulses. The experimental results are explained by dynamics of laser-excited radicals. The shape of fabricated structures demonstrates that thermal accumulation and oxygen diffusion from the surrounding air make an influence on polymerization when the pulse duration is in the nanosecond range. By using picosecond laser pulses, the thermal accumulation and oxygen diffusion effects are not important for low repetition rate (500 Hz), and they become relevant only at the repetition rates higher than ≥ 1 kHz. It is shown that thermal accumulation is caused by a low-temperature diffusivity and heat accumulation at the polymer-glass interface, and it plays a significant role in the final shape of the structures fabricated using the nanosecond laser pulses.