This paper describes a set of experiments which examine the feasibility of applying polarization diversity to a 12,760 km ionospheric link from Livingston Island (62.6°S, 60.4°W), South Shetlands, to Cambrils (41.0°N, 1.0°E), Spain. A transmitting monopole and both a monopole and a dipole (inverted-V) at reception are the antennas used in this measurement campaign. Receiving antennas are orthogonal polarized to check whether wave polarization rotation causes differences between simultaneous signals. The results gathered in the paper indicate that there is a marked difference between simultaneous signals at vertical and horizontal polarized antennas, which depends on the hour of the day and the signal frequency. In this low-throughput HF data link, polarization diversity could be used to increase SNR and performance through smart combination of receiving signals, due to the low cross-correlation factor between them.