Pyrethroids and organophosphates are among the most toxic insecticides for aquatic organisms, leading to annual-average environmental quality standards (AA-EQS) in the picogram per liter range in surface waters. For monitoring purposes, it is therefore crucial to develop very sensitive analytical methods. Until now, it is very difficult to reach detection limits at or below given AA-EQSs. Here, we present a passive sampling method using silicone rubber (SR) sheets for the sampling of ten pyrethroids and two organophosphates in surface waters. An analytical method was developed, optimized and validated for the extraction of the insecticides from the SR sheets by accelerated solvent extraction followed by clean-up on C18 and silica gel and detection with GC–MS/MS in positive ionization mode. Good precision (<20%) and absolute recovery (>50%) was observed for all substances, accuracy was between 66% and 139%. Limits of detection between 6 and 200 pg/L were achieved for all substances in surface waters using average sampling rates for PCBs and PAHs. The lack of substance-specific sampling rates and missing performance reference compounds led to an uncertainty in the concentration estimation of factor three in both directions. In a large field study, comprising 40 environmental samples from nine Swiss rivers, eight out of 12 substances were detected (most frequently: chlorpyrifos, cypermethrin). Most of the estimated organophosphate concentrations were between 0.1 and 1 ng/L, most pyrethroid detections below 0.1 ng/L. Four substances (chlorpyrifos-methyl, cypermethrin, deltamethrin and lambda-cyhalothrin) showed exceedances of their respective AA-EQS in multiple samples, also when the uncertainties in the concentration estimation were considered. As pyrethroid and organophosphate detection by SR passive sampling is very practicable and allows sensitive analysis, it has the potential to become a new tool in the monitoring of non-polar pesticides.