The development of a new, lower cost method for trace explosives recovery from complex samples is presented using miniaturised, click-together and leak-free 3D-printed solid phase extraction (SPE) blocks. For the first time, a large selection of ten commercially available 3D printing materials were comprehensively evaluated for practical, flexible and multiplexed SPE using stereolithography (SLA), PolyJet and fused deposition modelling (FDM) technologies. Miniaturised single-piece, connectable and leak-free block housings inspired by Lego® were 3D-printed in a methacrylate-based resin, which was found to be most stable under different aqueous/organic solvent and pH conditions, using a cost-effective benchtop SLA printer. Using a tapered SPE bed format, frit-free packing of multiple different commercially available sorbent particles was also possible. Coupled SPE blocks were then shown to offer efficient analyte enrichment and a potentially new approach to improve the stability of recovered analytes in the field when stored on the sorbent, rather than in wet swabs. Performance was measured using liquid chromatography-high resolution mass spectrometry and was better, or similar, to commercially available coupled SPE cartridges, with respect to recovery, precision, matrix effects, linearity and range, for a selection of 13 peroxides, nitramines, nitrate esters and nitroaromatics. Mean % recoveries from dried blood, oil residue and soil matrices were 79 ± 24%, 71 ± 16% and 76 ± 24%, respectively. Excellent detection limits between 60 fg for 3,5-dinitroaniline to 154 pg for nitroglycerin were also achieved across all matrices. To our knowledge, this represents the first application of 3D printing to SPE of so many organic compounds in complex samples. Its introduction into this forensic method offered a low-cost, ‘on-demand’ solution for selective extraction of explosives, enhanced flexibility for multiplexing/design alteration and potential application at-scene.