Solid silicon nanowires and their luminescent properties have been widely studied, but lesser is known about the optical properties of mesoporous silicon nanowires (mp-SiNWs). In this work, we present a facile method to generate greenish-blue photoluminescence (GB-PL) by fast scanning a focused green laser beam (wavelength of 532 nm) on a close-packed array of mp-SiNWs to carry out photo-induced chemical modification. The threshold of laser power is 5 mW to excite the GB-PL, whose intensity increases with laser power in the range of 5–105 mW. The quenching of GB-PL comes to occur beyond 105 mW. The in-vacuum annealing effectively excites the GB-PL in the pristine mp-SiNWs and enhances the GB-PL of the laser-modified mp-SiNWs. A complex model of the laser-induced surface modification is proposed to account for the laser-power and post-annealing effect. Moreover, the fast scanning of focused laser beam enables us to locally tailor mp-SiNWs en route to a wide variety of micropatterns with different optical functionality and we demonstrate the feasibility in the application of creating hidden images.