This study is the first to investigate the ingestion of microplastics (MPs), plasticizers, additives, and particles of micro-litter <100 μm by larvae of Simuliidae (Diptera) in rivers. Blackflies belong to a small cosmopolitan insect family whose larvae are present alongside river courses, often with a torrential regime, up to their mouths. Specimens of two species of blackfly larvae, Simulium equinum and Simulium ornatum, were collected in two rivers in Central Italy, the Mignone and the Treja. Small microplastics (SMPs, <100 μm), plasticizers, additives, and other micro-litter components, e.g., natural and non-plastic synthetic fibers (APFs) ingested by blackfly larvae were, for the first time, quantified and concurrently identified via MicroFTIR. The pretreatment allowed for simultaneous extraction of the ingested SMPs and APFs. Strong acids or strong oxidizing reagents and the application of temperatures well above the glass transition temperature of polyamide 6 and 6.6 (55–60 °C) were not employed to avoid further denaturation/degradation of polymers and underestimating the quantification. Reagent and procedural blanks did not show any SMPs or APFs. The method’s yield was >90%. Differences in the abundances of the SMPs and APFs ingested by the two species under exam were statistically significant. Additives and plasticizers can be specific to a particular polymer; thus, these compounds can be proxies for the presence of plastic polymers in the environment.