This work presents a novel application of gas-diffusion microextraction (GDME) for the extraction and identification of volatile carbonyl compounds from a dry-process fibreboard (MDF) by combining high-performance liquid chromatography with diode array detection (HPLC–DAD) and mass spectrometry (MS). GDME is a simple, inexpensive, and environmentally friendly technique that allows the simultaneous extraction and derivatization with 2,4-dinitrophenylhydrazine (DNPH) of selected volatiles. The extraction conditions were optimized using design of experiments through a 24 full fractional design followed by a Box–Behnken design, resulting in 35 min of extraction at 45 °C using 500 µL of DNPH 0.15%. The analysis of commercial MDF samples with different characteristics, such as thickness or colour, showed a distinct emission profile of volatile carbonyls. The principal emitting compounds found were formaldehyde, acetaldehyde, acetone, butanal, pentanal, hexanal, heptanal, octanal, and nonanal. A total of 25 compounds were identified using MS, including saturated and unsaturated aldehydes, ketones, dicarbonyls, and benzaldehyde-derivatives. This method can be a valuable tool for the qualitative evaluation of VOCs released from wood-based panels and for the assessment of indoor-air quality.