Samples of polymethylmethacrylate have been irradiated with laser pulses of 266 nm wavelength along with the wavelengths generated via hydrogen‐shifted stimulated Raman scattering. A quadrupole mass spectrometer monitors in real time the photoablation products produced during the irradiation. At wavelengths of 266 nm and above, the products are dominated by monomer, CO2, and CO. At wavelengths below 266 nm, a dramatic change of ablation products is observed, with methyl formate appearing as a major photochemical product.