Electrospun mats from nano/micro-fibers with controlled porosity and pore shape may be ideal candidate for tissue engineering scaffolds. In this study three types of poly(vinyl alcohol) (PVA) mats of 41 mu m - 66 mu m thickness with different average nano/micro-fibers diameter of 100 nm - 200 nm were deposited on spunbond polypropylene (PP) filaments by electrospinning process. Controlled density porosity in the electrospun mats was introduced by Yb:KGW femtosecond laser micromachining system. The influence of electrospun mat microstructure, the distance between the adjacent laser ablation points, the number of femtosecond laser pulses on quality and structure of the laser irradiated holes were investigated. It was demonstrated that the quality of irradiated holes depends on the structure of electrospun mats (diameter of nano/micro-fibers, thickness of mats) and femtosecond laser processing parameters. Varying the distance between points of laser irradiation as well as number of applied femtosecond laser pulses it is possible to fabricate electrospun mats with increased porosity having extra pores of 22 mu m - 36 mu m in diameter.