We report on the first results obtained from a new optical identification programme of 123 faint X-ray sources with S(0.5-2 keV) > 2 x 10(-14) erg s(-1) cm(-2) serendipitously detected in ROSAT PSPC pointed observations. We have spectroscopically identified the optical counterparts to more than 100 sources in this survey. Although the majority of the sample (68 objects) are QSOs, we have also identified 12 narrow emission line galaxies which have extreme X-ray luminosities (10(42) < L(X) < 10(43.5) erg s(-1)). Subsequent spectroscopy reveals them to be a mixture of starburst galaxies and Seyfert 2 galaxies in approximately equal numbers, Combined with potentially similar objects identified in the Einstein Extended Medium Sensitivity Survey, these X-ray-luminous galaxies exhibit a rate of cosmological evolution, L(X) proportional to (1 + z)(2.5+/-1.0), consistent with that derived for X-ray QSOs, This evolution, coupled with the steep slope determined for the faint end of the X-ray luminosity function (Phi(L(X)) proportional to L(X)(-1.9)), implies that such objects could comprise 15-35 per cent of the soft (1-2 keV) X-ray background.