Laser ablation technique has been successfully used for the deposition of CdSe and CdTe/CdSe multilayers on Si(100) and Si(l11) substrates. X-ray analysis showed that CdSe/Si films were highly oriented. Their orientation changed from (100) to (002) by varying the substrate temperature from 473 to 673K. High orientation was also obtained on multilayered polycrystalline structures of CdSe and CdTe on Si(lll). Photoluminescence experiments have also been carried out on the deposited films.