At the point when I applied to Automattic, I was working for Speck (phone and laptop case manufacturer) as a Senior eCommerce Developer specializing in Magento, and had been an active contributor to the WordPress open source project for probably about two years?
That being said, please don't think you need to know PHP to work at Automattic. I mean, it's useful, sure, but JS knowledge is huge as well, and we have some folks on our Data team that just do Python. Our Mobile team works pretty much purely in the languages for Android and iOS. Elasticsearch is something we also do huge amounts of work with (as @gibrown can testify)
If it's interesting to anyone, here's my resume as I submitted it with my application (with personal information redacted) (yes, I wrote it in markdown) -- https://gist.githubusercontent.com/georgestephanis/a5095ca4f...