The present study theoretically explored the feasibility of the capillary method for measuring near-infrared (NIR) spectra of liquid or solution samples with microlitre volume, which was proposed in our previous studies. Lambert-Beer absorb- ance rule was applied to establish a model for the integral absorbance of capillary, which was then implemented in numerical analyses of the effects of capillary on various spectral features and dynamic range of absorption measurement. The theoretical speculations indicated that the capillary method might be used in NIR spectroscopy, which was further supported by the empirical data collected from our experiments by comparison between capillary NIR spectra of several organic solvents and cuvette cell NIR spectra. The present study theoretically explored the feasibility of the capillary method for measuring near-infrared (NIR) spectra of liquid or solution samples with microlitre volume, which was proposed in our previous studies. Lambert-Beer absorb- ance rule was applied to establish a model for the integral absorbance of capillary, which was then implemented in numerical analyzes of the effects of capillary on various spectral features and dynamic range of absorption measurement. The theoretical speculations that that the capillary method might be used in NIR spectroscopy, which was further supported by the empirical data collected from our experiments by comparison between capillary NIR spectra of several organic solvents and cuvette cell NIR spectra.