Selenium supersaturated silicon layers were fabricated by pulsed excimer laser induced liquid-phase mixing of thin Se films on Si(001) wafers. Sufficiently low Se coverage avoids destabilization of rapid epitaxial solidification, resulting in supersaturated solid solutions free of extended defects, as shown by transmission electron microscopy. The amount of retained Se depends on the original film thickness, the laser fluence, and the number of laser pulses irradiating the same spot on the surface. Using this method, Se has incorporated into the topmost 300 nm of the silicon with a concentration of 0.1 at.%. Channeling Rutherford backscattering spectrometry measurements show that the substitutional fraction can be as high as 75% of the total retained Se. These alloys exhibit strong sub-band-gap absorption with optical absorption coefficient ranging up to about 104 cm−1, thus making them potential candidates for applications in Si-based optoelectronic devices.