Abstract The prime purpose of this work is to prepare a novel kind of Pickering interfacial solid catalysts for biodiesel production to meet the requirements of highly efficiency and environmental benign. To achieve this goal, the core–shell P[xSPA-yDABCO]@SiO2@Fe3O4 composite materials with a shell of photo-responsive and base catalytic sites were manufactured by means of layer-by-layer fabrication method. The modified materials, entirely characterized by transmission electron microscopy (TEM), scanning electron microscope (SEM), Fourier transform infrared (FT-IR) spectra, X-ray powder diffraction (XRD) and magnetization versus magnetic (VSM) techniques, demonstrated sufficient catalytic active sites and photo-responsive sites. Among all the so-prepared catalysts, P[3SPA-2DABCO]@SiO2@Fe3O4 performs extremely well and can stabilize soybean oil-in-methanol Pickering emulsion for 24 h, achieving a biodiesel yield up to 98.2% at a catalyst dosage of 5 wt% after the reaction time of 5 h at 60 °C. Furthermore, the double responsive solid catalyst can be readily separated from the mixture of reaction by an external magnet and UV irradiation, and still presented superior catalytic activity after 6 cycles.