Three types of molecularly imprinted solid‐phase microextraction fibers were fabricated through sol‐gel method using diazinon, parathion‐methyl, and isocarbophos as templates, respectively, and assembled together to construct a multifiber for analysis of organophosphorus pesticides in complex matrices. The multifiber provided large extraction capacity and high imprinting factor up to 3.89. In contrast, the imprinting factor of a single fiber was around 1.6, and the multi‐template imprinted coating showed no selectivity. The multifiber was applied to analyze pesticides in fruits and vegetables. The limits of detection, which ranged from 0.0052 to 0.23 µg/kg, were lower than those obtained by a single molecularly imprinted fiber, and much lower than those reported by other methods. The recoveries of five analytes in spiked apple, cucumber, Chinese cabbage, and cherry tomato samples were 75.1–123.2%. The study shows that the molecularly imprinted multifiber could achieve simultaneous selective extraction and sensitive determination of multiple targets in complex matrices for high‐throughput analysis.