Multi-functionalized rugate porous silicon (PSi) for biosensor was developed by hydrosilylation with silole and its further reaction with biotin groups. PSi was generated by an electrochemical etching of silicon wafer in aqueous ethanolic HF solution PSi prepared by using etching conditions showed that many sharp spectral lines can be obtained in the optical reflectivity spectrum. 1,1-hydrovinyl-2,3,4,5-tetraphenylsilole was obtained from the reaction of 1,1-dilithio-2,3,4,5-tetraphenyl-1,3-butadiene with dichlorovinylsilane. Multi-functionalized PSi with silole and biotin groups was characterized by UV-vis absorption spectroscopy, Ocean optics 2000 spectrometer, and fluorescence spectroscopy. Optical characteristics such as reflectivity and photoluminescence (PL) were observed. An increase of the reflection wavelength in the reflectivity spectrum by 20 nm was observed, indicative of a change in refractive indices induced by hydrosilylation of the silole and biotin groups to the rugate PSi. This red-shift was attributed to the replacement of some of the Si-H group of fresh rugate PSi with silole and biotin group.