The visible photoluminescence behaviour in pure and lithium doped porous silicon has been studied and the luminescent results obtained from the spectral analysis were discussed based on the hypothesis of quantum confinement model. Two different preparation methods, metal assisted electrochemical etching and metal assisted electro-less etching, were used for the fabrication pSi. The characteristic photoluminescence properties of porous silicon have been obtained effectively on porous silicon samples whose microstructure contains features of interconnected skeleton net work structure with localization of irregular quantum sized structures/pores. It is shown that there is a direct correlation between the visible luminescence emission properties and the etching durations. Electrochemical lithium intercalation enhances the photoluminescence intensity of porous silicon more than two orders of magnitude larger on compared to pure porous silicon and this photoluminescence enhancement may be attributed to the generation of large density of silicon quantum structures in lithium nested silicon pore walls. © 2020 Elsevier B.V., All rights reserved.