A novel DC-assisted fast hot-pressing (FHP) powder sintering technique was utilized to prepare Al/Diamond composites. Three series of orthogonal experiments were designed and conducted to explore the effects of sintering temperature, sintering pressure, and holding time on the thermal conductivity (TC) and sintering mechanism of an Al-50Diamond composite. Improper sintering temperatures dramatically degraded the TC, as relatively low temperatures (≤520 °C) led to the retention of a large number of pores, while higher temperatures (≥600 °C) caused unavoidable debonding cracks. Excessive pressure (≥100 MPa) induced lattice distortion and the accumulation of dislocations, whereas a prolonged holding time (≥20 min) would most likely cause the Al phase to aggregate into clusters due to surface tension. The optimal process parameters for the preparation of Al-50diamond composites by the FHP method were 560 °C-80 MPa-10 min, corresponding to a density and TC of 3.09 g cm⁻³ and 527.8 W m⁻¹ K⁻¹, respectively. Structural defects such as pores, dislocations, debonding cracks, and agglomerations within the composite strongly enhance the interfacial thermal resistance (ITR), thereby deteriorating TC performance. Considering the ITR of the binary solid-phase composite, the Hasselman–Johnson model can more accurately predict the TC of Al-50diamond composites for FHP technology under an optimal process with a 3.4% error rate (509.6 W m⁻¹ K⁻¹ to 527.8 W m⁻¹ K⁻¹). The theoretical thermal conductivity of the binary composites estimated by data modeling (Hasselman–Johnson Model, etc.) matches well with the actual thermal conductivity of the sintered samples using the FHP method.