We present the experimental evidence of structural surface modifications of poly(methyl methacrylate) (PMMA) caused by simultaneous action of extreme ultraviolet (XUV) (∼21 nm ) and visible-near infrared (visible-NIR) (820/410 nm) ultrashort pulses. Although the fluence of each individual beam was far below the surface modification threshold, very efficient and specific material expansion was observed after irradiation of PMMA by more than ∼20 shots of mixed XUV/visible-NIR radiation. As the XUV photons generate free charge carriers, absorption of the optical radiation dramatically increases, which heats up the material and further enhances the XUV induced damage to the polymer chain.