There are still no standardized processes, to address a comprehensive microplastic (MP) monitoring in real environmental scenarios. Such methods must process a high number of samples and large sample volumes time- and cost-efficiently. Especially for sediment samples, current methods lack representative sample volumes and masses. We want to introduce electrostatic separation (ES) as a method to overcome this problem. We applied ES to different particulate matrices such as quartz sand and various river sediments. Thus, we were able to derive a feasible working range of this method. Moreover, a comparison of recovery rates for different sample sizes, MP types and, contents was carried out. Nine different particulate matrices were used to investigate the particle size dependency of ES. Quartz sand samples (Cemex AG, Dresden, Germany) with a mass of 100 g and 1000 g were spiked with 75 mg of MP low-density polyethylene (LD-PE), polyethylene therephthalate (PET) and polycaprolactone (PCL; total MP mass per sample: 225 mg) in a size range of 63-200 µm. Additionally, 1000 g of quartz sand were spiked with different contents of LD-PE. MP quantification was carried out by differential scanning calorimetrie (DSC). Our results show a great potential of ES to enrich samples of quartz sand with an average particle size above 200 µm. Even small contents of finer particles seem not to have an influence on the separation result. MP was successfully separated form quartz sand by ES. The recoveries are in a moderate range for all MP types (50 to 100 %). In the range of 10 to 80 mg LD-PE per kilogram sand no significant differences of the recovery were found. The average recovery was 90 ± 8%. The theoretical limit of quantification was determined as 2.3 mg MP in 1 kg sediment. We conclude that ES can facilitate a fast and reliable extraction of MP from particulate matrices. The application of ES and DSC for MP analysis in river sediments shows a very high potential to address comprehensive monitoring time- and cost-efficiently. However, further research is required to address smaller particle sizes and more polymer types.