A furfural-based DOPO-containing flame retardant, 6,6′-(((methylenebis(4,1-phenylene))bis(azanediyl))bis(furan-2-ylmethylene))bis(dibenzo[c,e][1,2]oxaphosphinine 6-oxide) (MBF-DOPO), was synthesized and utilized as a co-curing agent of 4,4′-diaminodiphenyl methane (DDM) for fire-safe epoxy thermosets. For the cured epoxy resin containing 4.0% MBF-DOPO, the limiting oxygen index (LOI) reached 32.9% (with the V-0 rating in UL-94 test), and the peak heat release rate and total smoke production values were respectively decreased by 29.3% and 33.6%, compared to pure epoxy resin. Scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) results confirmed that the furfural-based flame retardant MBF-DOPO promoted the charring formation of the epoxy matrix, which effectively isolated the gas and heat transfer during combustion and thus enhanced the fire-safety performance of the epoxy thermosets. This work provides an effective route for synthesizing a furfural-based flame retardant, which possesses great potential for application in fire-safe epoxy thermosets.