Monitoring of laser-based processes is essential for ensuring the quality of produced surface structures and for maintaining the process stability and reproducibility. Optical methods based on scatterometry are attractive for industrial monitoring as they are fast, non-contact, non-destructive, and can resolve features down to the sub-microscale. Here, Laser-Induced Periodic Surface Structures (LIPSS) are produced on stainless steel using ultrashort laser pulses in combination with a polygon scanning system. After the process, the fabricated LIPSS features are characterized by microscopy methods and with an optical setup based on scatterometry. Images of the diffraction patterns are collected and the intensity distribution analyzed and compared to the microscopy results in order to estimate the LIPSS height, spatial period, and regularity. The resulting analysis allows us to study LIPSS formation development, even when its characteristic diffraction pattern gradually changes from a double-sickle shape to a diffuse cloud. The scatterometry setup could be used to infer LIPSS height up to 420 nm, with an estimated average error of 7.7% for the highest structures and 11.4% in the whole working range. Periods estimation presents an average error of ~5% in the range where LIPSS are well-defined. In addition, the opening angle of the LIPSS was monitored and compared with regularity measurements, indicating that angles exceeding a certain threshold correspond to surfaces where sub-structures dominate over LIPSS.