Bartholen's got it right. Here's a brief description of song structure [http://en.wikipedia.org/wiki/Song_structure_(popular_music)#Introduction] for you.
I know of only a couple songs that follow that structure, although not completely within the 'vocals only' format. Here's one of my favorite obscure bands, Flunk, a band from Norway, with the first track off of their debut (?) album. The introduction lasts approximately 40 seconds and is dominated by Anja Oyen Vister's vocals:
Flunk - Play
Another song, again with an introduction dominated by vocals, this time by lead singer Emily Haines, is Live it Out by Metric. The opening vocals last approximately 27 seconds:
Metric - Live it Out
I might as well add another as I absolutely love women who sing. Here's Killing by Olive, with pure vocals in the introduction, which lasts for 10 seconds:
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