This paper describes a possibility to control of laser ablation using material functionality. As an example, a remarkable difference is shown in the laser ablation of a polystyrene film coated with a photovoltaic perylene/phthalocyanine bilayer when compared with a bare polystyrene film after irradiation at an intensity range of 109 ∼ 1010W/cm2 (λ=1064 nm, 1.1-ns FWHM). Without the bilayer coating, the laser pulse formed spiky structures in the polystyrene film as self-focusing traces of the laser pulse, while for the coated film, the uniform surface ablation trace without the spiky interior structures was observed. The phenomena in the presence of the organic photovoltaic coating material agree with the required ablation to achieve high-density compression of the fuel capsule for inertial fusion energy.