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Afforestation processes, natural and anthropogenic, involve the conversion of other land uses to forest, and they represent one of the most important land use transformations, influencing numerous ecosystem services. Although remotely sensed data are commonly used to monitor forest disturbance, only a few reported studies have used these data to monitor afforestation. The objectives of this study were two fold: (1) to develop and illustrate a method that exploits the 1985–2019 Landsat time series for predicting afforestation areas at 30 m resolution at the national scale, and (2) to estimate afforestation areas statistically rigorously within Italian administrative regions and land elevation classes. We used a Landsat best-available-pixel time series (1985–2019) to calculate a set of temporal predictors that, together with the random forests prediction technique, facilitated construction of a map of afforested areas in Italy. Then, the map was used to guide selection of an estimation sample dataset which, after a complex photointerpretation phase, was used to estimate afforestation areas and associated confidence intervals. The classification approach achieved an accuracy of 87%. At the national level, the afforestation area between 1985 and 2019 covered 2.8 ± 0.2 million ha, corresponding to a potential C-sequestration of 200 million t. The administrative region with the largest afforested area was Sardinia, with 260,670 ± 58,522 ha, while the smallest area of 28,644 ± 12,114 ha was in Valle d’Aosta. Considering elevation classes of 200 m, the greatest afforestation area was between 400 and 600 m above sea level, where it was 549,497 ± 84,979 ha. Our results help to understand the afforestation process in Italy between 1985 and 2019 in relation to geographical location and altitude, and they could be the basis of further studies on the species composition of afforestation areas and land management conditions.