In this study, we evaluated the extraction effect of three different extractants, namely hexane + ether (v/v = 3:1), acetonitrile and ethyl acetate, on polycyclic aromatic hydrocarbons (PAHs) and phthalic acid esters (PAEs) in placenta detected and analysed by triple quadrupole gas chromatography–mass spectrometry (GC-MS/MS). The results showed that n-hexane + ether (v/v = 3:1) had the highest extraction efficiency. Under the optimal conditions, the limits of detection (LOD) for the 10 PAHs were 0.003–0.0167 μg/L with relative standard deviations (RSD) of 1.4–5.48% and detection rates of 68.19–107.05%, and the correlation coefficients were (R2, 0.9982–0.9999). The LODs for the nine PAEs were 0.0015–3.5714 μg/L and the correlation coefficients were (R2, 0.9982–0.9999). The limits of detection (S/N = 3) for the nine PAHs were 0.0015–0.5714 μg/L with relative standard deviations (RSD) of 3.15–8.37%, and the detection rates were 80.45–112.59% with correlations of (R2, 0.9972–0.9998). The method was applied to the analysis of PAHs and phthalates in placenta samples from pregnant women. The method’s accuracy and applicability were demonstrated. In comparison with other methods for the detection of PAEs and PAHs, the method proposed in this paper has a wider linear range, lower minimum detection limit and comparable recovery with good correlation. This paper is dedicated to providing another method for improving the performance of extracting solid tissues.