An analysis of the 22-yr ozone (O3) series (1988–2009) at the subtropical high mountain Izaña station (IZO; 2373 m a.s.l.), representative of free troposphere (FT) conditions, is presented. Diurnal and seasonal O3 variations as well as the O3 trend (0.19 ± 0.05% yr−1 or 0.09 ppbv yr−), are assessed. A climatology of O3 transport pathways using backward trajectories shows that higher O3 values are associated with air masses traveling above 4 km altitude from North America and North Atlantic Ocean, while low O3 is transported from the Saharan continental boundary layer (CBL). O3 data have been compared with PM10, 210Pb, 7Be, potential vorticity (PV) and carbon monoxide (CO). A clear negative logarithmic relationship was observed between PM10 and surface O3 for all seasons. A similar relationship was found between O3 and 210Pb, but only for the summer-time. The highest daily O3 values (90th percentile) are observed in spring and in the first half of summer-time. A positive correlation between O3 and PV, and between O3 and 7Be is found throughout the year, indicating that relatively high surface O3 values at IZO originate from the middle and upper troposphere. At IZO we find a~good correlation between O3 and CO in winter, supporting the hypothesis of long-range transport of photochemically generated O3 from North America. Aged air masses, in combination with sporadic inputs from the upper troposphere, are observed in spring, summer and autumn. In summer-time high O3 values seem to be the result of stratosphere-to-troposphere (STT) exchange processes in regions neighbouring the Canary Islands. Since 1995–1996, the North Atlantic Oscillation has changed from a predominantly high positive phase to alternating between negative, neutral or positive phases. This change results in an increased flow of the westerlies in the mid-latitude and subtropical North Atlantic, thus favouring the transport of O3 and its precursors from North America, and a~higher frequency of storms over North Atlantic, with a~likely higher incidence of STT processes in mid latitudes. These processes lead to an increase of tropospheric O3 in the subtropical North Atlantic region after 1996 that has been reflected in surface O3 records at IZO.