Due to the difficulty of creating directional fractures efficiently and accurately with existing non-explosive rock-breaking methods, a directional fracturing technique utilizing a coal-based solid waste expansive agent, termed the instantaneous expansion with a single fracture (IESF), has been developed. IESF can generate high-pressure gases within 0.05–0.5 s and utilize gas pressure to achieve directional rock fragmentation. The rock-breaking mechanisms under double-borehole conditions of conventional blasting (CB), shaped charge blasting (SCB), and IESF were studied by theoretical analysis, numerical simulation, and in situ test. The gas pressure distribution within directional fractures of IESF was determined, and the crack propagation criterion between double-borehole was established. Numerical simulation results indicated that the stress distribution in CB was random. SCB exhibited tensile stress of −10.89 MPa in the inter-borehole region and −8.33 MPa on the outer-borehole region, while IESF generated −14.47 MPa and −12.62 MPa in the corresponding regions, demonstrating that stresses generated between adjacent boreholes can be superimposed in the inter-hole region. In CB, strain was concentrated along main fractures. SCB exhibited strains of 7 mm and 8 mm in the shaped charge direction, while non-shaped charge directions showed a strain of 1.5 mm. For IESF, strain in the shaped charge direction measured 6 mm, compared to 1 mm in non-shaped charge directions, resulting in superior directional fracture control. In situ test results from Donglin Coal Mine demonstrated that IESF can form superior directional rock-breaking efficacy compared to both CB and SCB, with the average crack rates of 95.5% by IESF higher than 85.0% by SCB. This technique provides a non-explosive method that realizes precise control of the direction of cracks while avoiding the high-risk and high-disturbance problems of explosives blasting.