This paper presents a comparative study of direct laser ablation (DLA) and laser-induced plasma-assisted ablation (LIPAA) methods to fabricate single-channel microgrooves on the surface of glass substrate by picosecond laser irradiation. The comparative study focuses on the morphological feature and surface chemical components of the micro-groove generated. For this purpose, optical microscope, scanning electron microscope (SEM) and X-ray photoelectron spectroscopy (XPS) are utilized to characterize the changes of morphologic and chemical compositions. The influence of laser parameters on the morphology of the glass surface is explored. For DLA, the microgroove with the least quantity and size of cracks is prepared successfully by setting the parameters as: scanning speed of 1 mm/s at laser output power of 3 W. In case of LIPAA, microgroove with no cracks and greater depth is achieved by setting the parameters as: scanning speed of 1 mm/s at laser output power of 1 W and distance between glass substrate and copper target at 0.06 mm. The result of XPS demonstrates that there is no significant change in chemical elements on glass surface after DLA, while there is Cu element deposits on glass surface after LIPAA.