SummaryImproving the excitation conditions in two‐photon fluorescent lithography reduces the size of the fabricated structures to nanometre scales. We demonstrate that a precise control of the illumination profile and the scanning speed of the laser beam is enough to decrease the photo‐polymerization volume of resins by orders of magnitude. This work also shows experimental evidence of surface effects that yield a different polymerization intensity threshold compared with bulk. Such phenomenon enables to perform a non‐linear optical nanolithography in a simple way, allowing fast‐prototyping procedures. We present a detailed study of the polymer growth process using fluorescence and atomic force microscopy.