A review is made in this paper on the recent advances of the photo‐ and electro‐luminescence properties of porous silicon (PS). We start by describing the electrochemical formation mechanisms of PS, followed by the most significant results obtained by different structural and chemical characterization techniques. Next we discuss the origin of the strong visible photoluminescence observed at room temperature in PS. Finally the possibility of using PS structures as electroluminescent devices and photodetectors is discussed. For this application the use of transparent conductive polymer films as electrical contacts to PS is considered.