The primary liquid alcohols from ethanol to 1-hexanol were studied utilizing the configurational-bias Monte Carlo (MC) simulations of the modeled alcohols (transferable potential for phase equilibria-united atom model) and the small-angle X-ray scattering (SAXS) method. A novel approach for calculating the scattering intensities from the theoretically obtained MC data by utilizing the Debye equation and their further validation with experimental results was introduced. This procedure is important, since the common problem of how to initially separate the intra- and intermolecular contributions to the scattering when comparing the calculated and experimental data was successfully avoided. Nevertheless, the intra- and intermolecular contributions to the scattering were able to be investigated directly from the MC results. The most pretentious task of the procedure was the suppression of the MC box background scattering, which was solved by utilizing the averaging of the scattering intensities over the different box sizes. This method of the scattering intensity calculations enabled us to make a theoretical analog to the well-known small-angle neutron scattering contrast matching experiment that, in our case, nicely revealed the origin of the two alcohol scattering peaks in the SAXS regime of the scattering curves (0.3 A(-1) < q < 3 A(-1)). For the example of butanol, the outer alcohol scattering peaks at similar to 1.40 A(-1) were unambiguously ascribed to the correlations between the alcohol hydrocarbon tails described by the g(CH)x(CH)x(r) pair correlation function. Similarly, the inner alcohol scattering peaks that shift from similar to 0.8 to similar to 0.4 A(-1) with an increasing alkyl chain length of the alcohol molecule are mainly the consequence of the O-O correlations. These findings were tested on pentanol/water mixtures and further applied to the results of the structural investigations on the binary and ternary microemulsion systems of the nonionic surfactant Brij 35 (Tomsic, et al. J. Phys. Chem. B 2004, 108, 7021; Tomsic, et al. J. Colloid Interface Sci. 2006, 294, 194), which were in fact the actual motivation for this present study.