Cyanobacteria are microorganisms that are well-adapted to sudden changes in their environment, namely to light conditions. This has allowed them to develop mechanisms for photoprotection, which encompass alteration in pigment composition. Therefore, light modulation appears to be a suitable strategy to enhance the synthesis of specific pigments (e.g., phycocyanin) with commercial interest, in addition to conveying a more fundamental perspective on the mechanisms of acclimatization of cyanobacterium species. In this study, Synechocystis salina was accordingly cultivated in two light phase stages: (i) white LED, and (ii) shift to distinct light treatments, including white, green, and red LEDs. The type of LED lighting was combined with two intensities (50 and 150 µmolphotons·m−2·s−1). The effects on biomass production, photosynthetic efficiency, chlorophyll a (chl a) content, total carotenoids (and profile thereof), and phycobiliproteins (including phycocyanin, allophycocyanin, and phycoerythrin) were assessed. White light (under high intensity) led to higher biomass production, growth, and productivity; this is consistent with higher photosynthetic efficiency. However, chl a underwent a deeper impact under green light (high intensity); total carotenoids were influenced by white light (high intensity); whilst red treatment had a higher effect upon total and individual phycobiliproteins. Enhanced PC productivities were found under modulation with red light (low intensities), and could be achieved 7 days earlier than in white LED (over 22 days); this finding is quite interesting from a sustainability and economic point of view. Light modulation accordingly appears to be a useful tool for supplementary studies pertaining to optimization of pigment production with biotechnological interest.