It could work. You've got to think about two things:
1) Are these developed stories (even as one-shots, which could work REALLY well; a collection of one-shots) that you have a strong sense of desire to write? Do you care so much for the characters and their lives that you want to delve more into their selves?
2) Are your readers clamoring for these stories? Have you created such vibrant, full characters that you know people want to see more in a behind-the-scenes kind of way?
If the answer to both of those is yes, then... go for it. You should primarily write for YOU, but writing because your audience demands it is good, too.
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