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I'll assume you mean in the extracellular space, and not inside the muscle cells. Acetylcholine is the neurotransmitter released from motor end-plates to trigger muscle contraction. So it anything BUT relaxes muscles. High levels of Ca ions on the other hand, make the muscle fibers unable to respond to stimuli, so effectively relax the muscle. (Intracellular Ca release causes contraction though!)

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Q: What relaxes muscles more ACh or calcium ions?
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