Synthesis of silver nanoparticles (Ag NPs) using microalgae is gaining recognition for its environmentally friendly and cost-effective nature while maintaining high activity of NPs. In the present study, Ag NPs were synthesized using a methanolic extract of Chlorella vulgaris and subjected to calcination. The X-ray diffraction (XRD) analysis showed a crystalline nature of the products with AgO and Ag phases with an average crystalline size of 16.07 nm before calcination and an Ag phase with 24.61 nm crystalline size after calcination. Fourier transform infrared spectroscopy (FTIR) revealed the capping functional groups on Ag NPs, while scanning electron microscopy (SEM) displayed their irregular morphology and agglomeration after calcination. The organic coating was examined by energy-dispersive X-ray spectroscopy (EDX) and thermogravimetric (TGA) analyses, confirming the involvement of the metabolites. The UV-Vis analysis showed a difference in optical properties due to calcination. Synthesized Ag NPs were applied for the photodegradation of hazardous dye Brilliant Blue R in visible light. Different values of light intensity, catalyst dose, initial dye concentration, and pH were tested to identify the optimal set of operating conditions. The highest degradation efficiency of 90.6% with an apparent rate constant of 0.04402 min was achieved after 90 min of irradiation in the highest tested catalyst dosage.