A new process of magnetorheological figuring (MRF) based on the deliquescence theory is proposed to finish KDP crystals. A novel, non-aqueous, and abrasive-free magnetorheological (MR) fluid is explored, and polishing experiments are performed on a self-developed MRF machine. The removal mechanism is reckoned to be the result of a combination of dominant chemical etching and accessorial mechanical drag. The results indicate that the surface roughness of I plate KDP of 80×80 (mm) polished by MRF is 1.2 nm (root mean square (RMS)), and the tool marks are completely removed. The surface accuracy by MRF is 0.035\lambda (RMS), and the low/middle-frequency errors are significantly corrected after MRF.