The compounds of the doubly ordered perovskite family NaLnCoWO(6) (Ln = Y, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, and Yb) were synthesized by solid-state reaction, nine of which (Ln = Y, Sm, Eu, Gd, Tb, Dy, Ho, Er, and Yb) are new phases prepared under high-temperature and high-pressure conditions. Their structural properties were investigated at room temperature by synchrotron Xray powder diffraction and neutron powder diffraction. All of them crystallize in monoclinic structures, especially the nine new compounds have the polar space group P2(1) symmetry, as confirmed by second harmonic generation measurements. The P2(1) polar structures were decomposed and refined in terms of symmetry modes, demonstrating that the polar mode is induced by two nonpolar modes in a manner of Hybrid Improper Ferroelectricity. The amplitudes of these three major modes all increase with decreasing the Ln cation size. The spontaneous ferroelectric polarization is estimated from the neutron diffraction data of three samples (Ln = Y, Tb, and Ho) and can be as large as similar to 20 mu C/cm(2.)