As the ozone is one of the most relevant variables in the climate system, to get further in its long-term characterization is a critical issue. In this study, measurements of total ozone column (TOC) from five well-calibrated Brewer spectrophotometers placed in the Iberian Peninsula are analyzed. The ozone recovery is observed for the period 1993-2012, with a significant positive trend of +9.3 DU per decade in Central Iberian Peninsula. However, the low TOC levels during 2011 and 2012 over the study region notably reduce the rate of the TOC temporal trend. Empirical linear relationships are established between TOC and pressure, height, and temperature of the tropopause. The three linear fits showed seasonal and latitudinal dependence, being the relationships stronger during winter and spring months. Events with the presence of a double tropopause (DT) are proved to be characteristic of the study region. The decrease in TOC levels when these anomalous events occur is quantified around 10% in winter and spring with respect to the usual cases with a single tropopause. The total weight of the DT events with respect to the annual values is about 20%, with a negligible occurrence in summer and autumn and being latitudinal-dependent. The North Atlantic Oscillation (NAO) index explains the 30% of the total ozone variability in winter. The DT events are found to be more frequent with a positive phase of NAO index.