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In this study, the structural, morphological, and magnetic properties and the local structure of Bi_1−<i>x</i>La<i>_x</i>Fe_0.95Co_0.05O₃ (<i>x</i> = 0.05, 0.10, 0.15, 0.20) nanoparticles were systematically investigated. In the (La, Co) co-doped BiFeO₃ samples, a structural transition from a rhombohedral to orthorhombic structure was observed via X-ray diffraction. This structural phase transition resulted in significantly improved magnetic properties (<i>M</i>_s = 1.706 emu/g at 60 kOe). SEM analysis revealed that grain size decreased with increasing La concentration. The magnetic hysteresis loops confirmed that the significant enhancement of magnetization for all samples. Finally, combining the experimental synchrotron radiation techniques, we studied the samples’ local structure in order to analyze the reasons why the samples’ magnetic properties were enhanced.