For employing optimized wavelengths, a near-infrared (NIR) tomographic imaging system with multiwavelengths in a continuous wave (CW) enables us to provide accurate information of chromophores. In this paper, we discuss wavelength optimization with a selection from commercial laser diodes. Through theoretical analysis, the residual norm (R) and the condition number (κ) represent the uniqueness of a matrix problem and the smooth singular-value distribution of each chromophore, respectively. The optimum wavelengths take place for large R and small κ. We considered a total of 38 wavelengths of laser diodes in the range of 633-980 nm commercially available to discover optimum sets for a broad range of chromophore combinations. In the 38 wavelengths, there exists 501,942 (C538), 2,760,681 (C638), and 12,620,256 (C738) combinations of five, six, and seven wavelength sets, respectively, for accurately estimating chromophores (HbO2, HbR, H2O, and lipids), water, lipids, and the scattering prefactor A. With the numerical calculation, the top 10 wavelength sets were selected based on the principle of large R and small κ. In the study, the chromophore concentration for young and elderly women are investigated; finally, choosing the laser diodes with a wavelength of 650, 690, 705, 730, 870/880, 915, and 937 nm is recommended either for young or elderly women to construct a spectral NIR tomographic imaging system in the CW domain. Simulated data were used to validate the claims.