Hypnotism is in old time radio shows is often used by the villains. Like ventriloquism, hypnosis is a skill that can be learned and developed. However, there would be some very short episodes if a good guy was able to reform all the No-goodniks by swinging a pocket watch in front of them.
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The popular perception is that hypnosis is a form of unconsciousness, and therefore, similar to sleep. Supposedly, while under hypnosis, the subject is particularly vulnerable to suggestion, and this is the power that gives the villain an advantage. In fact, the subject is very awake, in a highly focused state. The focus can be so intense as to cause physical relaxation. This can be particularly useful in psychotherapy.
There are a few rules to hypnotism in literature (or on the radio). There is usually a “Stronger mind” imposing its will on a weaker subject. Supposedly, the subject cannot be hypnotized if they do not want to be. For this reason, the bad guy often tricks his subjects into allowing hypnosis.
The Man of Steel, of course, is too strong willed to be placed under hypnosis himself, but those Superman cares about the most are not so fortunate. This is the case with Lois Lane in “Black Narcissus”.
Hypnosis is used on pretty, naive girls who eventually find themselves under Boston Blackie's protection, but they only receive that protection after murder has occurred.