Vibrational spectroscopy is utilized to determine compounds. However, it has never been applied to quantify architecture of multicell biological specimens. By using Fourier transform Raman spectroscopy coupled with multivariate data analysis and wood meal samples of Eucalyptus camaldulensis and E. globulus trees, cell width and cell wall thickness of vessels and fibers, which mainly constitute hardwood xylem, were successfully quantified with correlation coefficients >0.8, both in the calibration and in the prediction against microscopically measured values for all traits. The important frequencies were found to contain wood chemical and physical information.