A phosphomolybdate has the molecular formula of K4M5P4Mo4HO27, and has the powder frequency-doubling intensity the same as that of KDP; when M is K, the phosphomolybdate is potassium hydrogen phosphomolybdate, the crystal belongs to a tetragonal system, the space group is I-4c2, unit cell parameters comprise a=9.670 angstroms, c=29.335 angstroms, alpha=beta=gamma=90 DEG and Z=4, and the unit cell volume is V=2743.1 cubic angstroms; when M is Rb, the phosphomolybdate is rubidium potassium hydrogen phosphomolybdate, the crystal also belongs to a tetragonal system, the space group is I-4c2, unit cell parameters comprise a=9.768 angstroms, c=29.635 angstroms, alpha=beta=gamma=90 DEG and Z=4, and the unit cell volume is V=2827.7 cubic angstroms; the two crystals are both grown by a fluxing agent spontaneous nucleation method or a fluxing agent top seed crystal method; the two crystals both have the nonlinear optical effect, and are incongruent melting compounds; and the two crystals as nonlinear optical crystals from infrared band to ultraviolet band can be used for preparation of a laser output frequency conversion laser device or used for preparation of a generator for generating a second, third, fourth or fifth harmonic generation harmonic to a laser beam with the wavelength of 1064 nm.