The decoupled charge structure is often used in controlled blasting. However, in actual engineering scenarios, boreholes are typically horizontal or inclined. The explosive is close to the borehole wall because of gravity action, resulting in an eccentric charge structure. In this study, concentric and eccentric decoupled charge blasting tests were conducted on 250 mm × 250 mm × 150 mm cuboid concrete specimens. The blast-induced fracture propagation behavior was evaluated using digital image correlation (DIC) technology, and surface fracture networks were extracted by image processing to investigate the fractal characteristics. A three-dimensional finite element model was established and verified using experimental data to reveal the influencing mechanism of the coupling medium and eccentricity coefficient on concrete fractures from the energy perspective. Finally, the borehole wall pressure (BWP) and displacement distribution with different charge structures and coupling media are analyzed theoretically, and the application of an eccentric charge structure in smooth blasting is discussed. The results reveal that nonequivalent BWP and displacement are produced in eccentric charge blasting, with a more evident crushed zone appearing on the coupled side owing to the higher energy utilization efficiency of the explosive. Sand had the largest fracture volume fraction ratio between the coupled and decoupled sides, effectively controlling the damage level on the decoupled side. The proposed eccentric decoupled charge-blasting scheme produced directional damage effects in the field test, maximizing the failure of the excavation rock while reducing the damage level to the reserved rock.