@HalfPint I was also grateful for the answer. I had a couple of those brightly coloured silicone trivet-type things we all use to pick up hot pots from the oven. Accidentally left them in a hot oven for a few minutes and they reeked of chemical and plastic so badly I had to throw them out. Hadn't realized there were different qualities of silicone on the market. Lesson learned.
The short answer: yes. Silicone can withstand temps up to 450F: ok for cakes and cookies, not ok for breads & high temp baking. It's inert so it leech into food, e-mit fumes, and is non-reactive, according to the FDA. That said, pure silicone is pretty darn safe. It's the low quality silicone cookware with fillers that may not be as safe. You can tell if there's a filler by twisting the molds. If there's any white color, it's not pure silicone and it might have all those problems that people have noticed about 'silicone cookware' like burning smells during baking. Get your molds from a reputable maker and you don't have much to worry about.
BTW: one of the drawbacks of silicone pans is its flexibility which can be problem when you've got a hot liquid mixture in the silicone. It can flop over and spill, causing burns. Put your pans and molds on a baking sheet to avoid this and don't over fill.
I re-read your question and wanted to add that, you should check to make sure that your molds are oven-safe. If they are made of pure silicone, it should be just fine for baking. Otherwise, there's a filler and the twist test should let you know.
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BTW: one of the drawbacks of silicone pans is its flexibility which can be problem when you've got a hot liquid mixture in the silicone. It can flop over and spill, causing burns. Put your pans and molds on a baking sheet to avoid this and don't over fill.