Optical spectral analysis of closely spaced, subcarrier multiplexed fiber-optic transmission is performed, based on stimulated Brillouin scattering (SBS). The Brillouin gain window of a single, continuous-wave pump is scanned across the spectral extent of the signal under test. The polarization pulling effect associated with SBS is employed to improve the rejection ratio of the analysis by an order of magnitude. Ten tones, spaced by only 10 MHz and each carrying random-sequence on-off keying data, are clearly resolved. The measurement identifies the absence of a single subcarrier, directly in the optical domain. The results are applicable to the monitoring of optical orthogonal frequency domain multiplexing and radio over fiber transmission.