No. The 100% chance means that 100% of the time she'll attempt to apply it. Each character also has a tenacity stat that gives them a chance to resist detrimental effects. I believe there are a handful of rare effects that bypass tenacity but they say that in the description.
Thanks for that answer Qeltar. It explains a lot. I was wondering why my Lumi's 85% never seemed to land. I'm so used to Dooku's 100% counter attack being 100%, that I didn't stop to think about how the percentages of other abilities are applied.
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