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Here's a Slate that claims Grimek and Paul Anderson were on the first steroids: article (link).
Here's an ad for methyl testosterone (link) you could buy in the 1940s.
Here's a steroids article (link) on a blog concerning their history. I'm thinking the Slate article might be more trustworthy than this blog article.
Maybe take this last article with a grain of salt. I think most people assume Reg Park was on steroids:
Here's a fascinating article (link) from the journal of sports history concerning steroids in the sixties.