You can simply capture the character before the slash in a group and use that in the replacement, for example:
"/hello/world".gsub(/([^\/])\//, '\1%2F') #=> "/hello%2Fworld"
Or if you just want to match any /
that appears after the first character, you can simplify this to:
"/hello/world".gsub(/(.)\//, '\1%2F') #=> "/hello%2Fworld"
Or like this:
"/hello/world".gsub(/(?<!^)\//, '%2F') #=> "/hello%2Fworld"