A simple method using 800-nm femtosecond laser irradiation and chemical selective etching has been proposed for fabrication of high-aspect-ratio all-silicon grooves. Grooves with the maximum aspect ratio of 44 were produced. A scanning electronic microscopy equipped with an energy dispersive X-ray spectroscopy was employed to characterize the morphology and chemical composition of the grooves respectively. The formation mechanism of the grooves was attributed to the chemical reaction of the laser induced refractive index change microstructures and hydrofluoric acid solution. The dependences of the aspect ratio of the grooves on the laser irradiation parameters, such as: the numerical aperture of the microscope objective lens, the laser average power and the laser scanning velocity, are discussed. (C) 2013 Elsevier B. V. All rights reserved.