Metabolite profiling of rice leaves (Oryza sativa cv. Ilmi) was performed to investigate the short-term responses to different light-emitting diode (LED) lights, blue (B), green (G), red (R), white (W), shade (S), by using gas chromatography-ion trap-mass spectrometry (GC-IT-MS) and ultra-performance liquid chromatography-quadrupole-time-of-flight-mass spectrometry (UPLC-Q-TOF-MS) with multivariate analysis. Clear grouping patterns of each light-grown sample, except G and W, were shown in partial least squares-discriminant analysis (PLS-DA). Thirty-two primary metabolites and eleven secondary metabolites were selected and visualized using heatmap. Antioxidant activities of rice leaves followed the order B=W=G>R>S and isoorientin-2''-O-glucoside, isovitexin-2''-O-glucoside, isoorientin-2''-O-(6'''-ρ-coumaroyl)-glucoside, and isoscoparin-2''-O-glucoside showed similar relative differences and had higher Pearson's correlation coefficients than other metabolites in correlation network. According to the orthogonal projection to latent structures-discriminant analysis (OPLS-DA) between B and R, the levels of amino acids, organic acids, fatty acids, and flavonoid glycosides were relatively high in B, whereas the glucose and fructose levels were high in R.