New management and techniques to reduce soil and water losses are necessary to achieve goals related to sustainability and develop useful agronomical plans. Among the strategies to reduce soil losses, the use of polymers has been studied but little is known about the effect of them on soil aggregates under extreme rainfall conditions. The main aim of this study was to compare the effects of polyacrylamide (PAM) and polyvinyl alcohol (PVA) on initial soil erosion process activation. We applied both products on soils and soil aggregate stability was measured on polymer treated and control plots. Laboratory erosion plots (pans) were placed on 15% slope, and sequential simulated rainfalls (under dry and wet conditions) with 360 mm h−1 intensity were applied for 12 min. Time to runoff, total runoff, runoff sediment yield, and splash sediment yield were determined. The results show that polymers do not delay runoff initiation; however, they reduced total runoff, sediment yield, and soil transported by the splash. PVA was not effective in reducing the total runoff during the first rainfall being PAM more effective in this way. However, under the sequential rainfall, both polymers obtained positive results, showing PAM some improvements in comparison to PVA. The effect of the polymer to reduce soil transported by splash after performing the second rainfall simulation was clearly demonstrated, meanwhile the effects during the first simulation were not significant. The effectiveness of the polymers on soil aggregates increased with increasing aggregate size. The application of polymers reached the highest efficiency on aggregates of 6.4 mm in diameter.