Direct supervisor quit company, can I still use them as an employment reference?

I'm filling out job applications but struggling to add details about professional references. My direct supervisor at my previous job was the only person who had comprehensive knowledge of my work ethic, professional character etc. They've since joined another company and I don't trust HR or upper level management at my old firm to write me a good reference since none of them actually know my work and are fairly difficult people. I don't have any other recent work references, only an academic one from university.

Should I get in touch with my old supervisor and ask to use her personal email address for the reference? How would I list her on my CV or application form, i.e. use her previous position at the firm?

Thanks x

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