You maybe need admin rights. Start cmd with admin rights, type "set" or "path" and hit enter in the cmd window. You will get a report about your environment variables. Take a look to the "Path=" section. There should be an entry like
C:\Program Files\Calibre2\
or
C:\Program Files (86)\Calibre2\
for calibre if you have a local installation.
If not, you probably run a portable version with a linked program icon. You can right-click this link and look for its properties.
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