Xandria released a solid goth metal demo in 2000, including both clean male and female vocals. The emphasis was on emotive quality over technicality, as is common to the genre. Later, they re-recorded some of those songs and others for a full-length debut under the same title "Kill the Sun". I haven't heard that release, but I know that they discontinued the use of male vocals, leaving only the beautiful female vocals of Lisa Schaphaus.
Although I personally haven't followed them since then, they have become a pretty major player in the gothic metal scene, with generally positive reviews coming from fans of Within Temptation and others.