We have analyzed the dynamics of the rice etioplast membrane proteome during the early phase of de-etiolation using iTRAQ-based relative protein quantification. Several hundred plastid proteins were identified from enriched membranes, including 36 putative transporters. Hierarchical clustering revealed the coordinated light induction of thylakoid membrane proteins with proteins involved in translation and fatty acid metabolism. No other functional category of identified proteins showed a similarly consistent light induction, and no consistent changes were observed for the identified transporters. This suggests that the etioplast metabolism is already primed to accommodate the metabolic changes that occur during the onset of photosynthesis. This hypothesis was further tested in metabolite profiling experiments. Here, the changes upon illumination are mostly restricted to a decrease in the concentration of some amino acids and an increase in the concentrations of aspartic acid, malic acid, fumaric acid, and succinic acid. These changes are consistent with a rapid activation of photosynthesis and subsequent rapid production of storage carbohydrates and proteins. The information at the proteome level and the parallel measurements of metabolite accumulation both support the view that only minor metabolic network reconstruction and modification of enzyme levels occurs during the first 4 h of etioplast to chloroplast differentiation.