Isocyanates are reactive semivolatile contaminants that must be assessed in occupational environments, and specific evaluation methods are required to address the challenges related to isocyanate emission characteristics. Several standard methods exist, but significant differences remain regarding the diversity of industrial isocyanate emissions. This study presents a method to establish a baseline comparison of three sampling principles. A fine aerosol (mass median aerodynamic diameter of 250 nm) of pure methylene diphenyl diisocyanate (MDI) was produced (5–60 μg m⁻³) using a laboratory generation system (n = 31 generation experiments). Airborne MDI was measured with the following four methods, with an emphasis on the spatial distribution of the collected MDI within the sampler: (1) Swinnex cassette 13 mm, glass fibre filter (GFF), 9-(N-methylaminomethyl) anthracene (MAMA-Swin); (2) closed-face cassette (CFC) 37 mm, GFF (end filter and inner walls), MAMA-37; (3) impinger and backup GGF, 1,2-methoxyphenylpiperazine (MP) (ISO 16702/MDHS 25); and (4) denuder and GFF (Asset EZ4-NCO), dibutylamine (DBA) (ISO 17334-1). Bland and Altman analyses determined that there were no significant bias between the methods although Asset was not in agreement with MAMA-Swin (95% confidence interval above the ±20% criteria). Significant correlations (P < 0.05) were observed between airborne MDI concentration levels and their distribution within the Asset (denuder vs. end filter) and impinger (collecting solution vs. backup filter) subsections. The presence of impregnated inner walls in the CFC did not increase collection efficiency for the generated MDI aerosol. Non-uniform MAMA impregnation on GFF was demonstrated, whereas the collected MDI was evenly distributed in the air samples. These results provided the basis of comparison for other studies involving more complex isocyanate emissions.