This paper presents the first results of comparison of Planck along with IRAS data with Green Bank Telescope 21-cm observations in 14 fields covering more than 800 square degrees at high Galactic latitude. Galactic dust emission for fields with average HI column density lower than 2 x 10^20 cm^-2 is well correlated with 21-cm emission. The residual emission in these fields, once the HI-correlated emission is removed, is consistent with the expected statistical properties of the cosmic infrared background fluctuations. Fields with larger column densities show significant excess dust emission compared to the HI column density. Regions of excess lie in organized structures that suggest the presence of hydrogen in molecular form, though they are not always correlated with CO emission. Dust emission from intermediate-velocity clouds is detected with high significance. Its spectral properties are consistent with, compared to the local ISM values, significantly hotter dust (T~20 K), lower sub-millimeter dust opacity, and a relative abundance of very small grains to large grains about four times higher. These results are compatible with expectations for clouds that are part of the Galactic fountain in which there is dust shattering and fragmentation. Correlated dust emission in HVCs is not detected; the average of the 99.9% confidence upper limits to the emissivity is 0.15 times the local ISM value at 857 and 3000 GHz, in accordance with gas phase evidence for lower metallicity and depletion in these clouds. Unexpected anti-correlated variations of the dust temperature and emission cross-section per H atom are identified in the local ISM and IVCs, a trend that continues into molecular environments. This suggests that dust growth through aggregation, seen in molecular clouds, is active much earlier in the cloud condensation and star formation processes.

30 pages, 22 figures, accepted for publication in A&A as a special issue for Planck early papers