The Planck survey provides unprecedented full-sky coverage of the submillimetre polarized emission from Galactic dust, bringing new constraints on the properties of dust. The dust grains that emit the radiation seen by Planck in the submillimetre also extinguish and polarize starlight in the optical. Using ancillary catalogues of interstellar polarization and extinction of starlight, we obtain the degree of polarization, $p_V$, and the optical depth in the $V$ band to the star, $\tau_V$. We extract the submillimetre polarized intensity, $P_S$, and total intensity, $I_S$, measured toward these stars in the Planck 353 GHz channel. We compare the position angle measured in the optical with that measured at 353 GHz, and the column density measure $E(B - V)$ with that inferred from the Planck product map of the submillimetre dust optical depth. For those lines of sight suitable for this comparison, we measure the polarization ratios $R_{S/V} = (P_S/I_S)/(p_V/\tau_V)$ and $R_{P/p} = P_S / p_V$ through a correlation analysis. We find $R_{S/V} = 4.3$ with statistical and systematic uncertainties 0.2 and 0.4, respectively, and $R_{P/p} = 5.6$ MJy sr$^{-1}$, with statistical and systematic uncertainties 0.2 and 0.4 MJy sr$^{-1}$, respectively. Our estimate of $R_{S/V}$ is reasonably compatible with current dust models, not yet very discriminating among them. However, the observed $R_{P/p}$ is a more discriminating diagnostic for the polarizing grain population and is not compatible with predictions of dust models, the observations being higher by a factor of about 2.5. These new diagnostics from Planck, including the spectral dependence in the submillimetre, will be important for constraining and understanding the full complexity of the grain models, and for further interpretation of the Planck thermal dust polarization.