A new selective and sensitive liquid chromatography triple quadrupole mass spectrometry method was developed for simultaneous analysis of natural pyrethrins and synthetic pyrethroids residues in baby food. In this study, two sample preparation methods based on ultrasound-assisted dispersive liquid–liquid microextraction (UA-DLLME) and salting-out assisted liquid–liquid extraction (SALLE) were optimized, and then, compared regarding the performance criteria. Appropriate linearity in solvent and matrix-based calibrations, and suitable recoveries (75–120%) and precision (RSD values ≤ 16%) were achieved for selected analytes by any of the sample preparation procedures. Both methods provided the analytical selectivity required for the monitoring of the insecticides in fruit-, cereal- and milk-based baby foods. SALLE, recognized by cost-effectiveness, and simple and fast execution, provided a lower enrichment factor, consequently, higher limits of quantification (LOQs) were obtained. Some of them too high to meet the strict legislation regarding baby food. Nonetheless, the combination of ultrasound and DLLME also resulted in a high sample throughput and environmental-friendly method, whose LOQs were lower than the default maximum residue limit (MRL) of 10 μg kg−1 set by European Community for baby foods. In the commercial baby foods analyzed, cyhalothrin and etofenprox were detected in different samples, demonstrating the suitability of proposed method for baby food control.