The purpose of this work was to develop a highly selective, sensitive, and reliable method for multi-residual analysis. A three-dimensional microporous reduced graphene oxide/polypyrrole nanotube/magnetite hydrogel (3D-rGOPFH) composite was synthesized and utilized as a magnetic solid-phase extraction (MSPE) sorbent to preconcentrate thirteen insecticides, including five organophosphorus (isocarbophos, quinalphos, phorate, chlorpyrifos, and phosalone), two carbamates (pirimor and carbaryl), two triazoles (myclobutanil and diniconazole), two pyrethroids (lambda-cyhalothrin and bifenthrin), and two organochlorines (2, 4′-DDT and mirex), from vegetables, followed by gas chromatography-tandem mass spectrometry. This method exhibited several major advantages, including simultaneous enrichment of different types of insecticides, no matrix effect, high sensitivity, and ease of operation. This is ascribed to the beneficial effects of 3D-rGOPFH, including the large specific surface (237 m2 g−1), multiple adsorption interactions (hydrogen bonding, electrostatic, π–π stacking and hydrophobic interaction force), appropriate pore size distribution (1–10 nm), and the good paramagnetic property. Under the optimal conditions, the analytical figures of merit were obtained as: linear dynamic range of 0.1–100 ng g−1 with determination coefficients of 0.9975–0.9998; limit of detections of 0.006–0.03 ng g−1; and the intra-day and inter-day relative standard deviations were 2.8–7.1% and 3.5–8.8%, respectively. Recoveries were within the range of 79.2 to 109.4% for tomato, cucumber, and pakchoi samples at the fortification levels of 5, 25, and 50 ng g−1. This effective and robust method can be applied for determining multi-classes of insecticide residues in vegetables.