In grad school this worked for me a few times, though I was not at a startup but rather contacting them re a topic of mutual interest. One was a VP at a top-5 b

In grad school this worked for me a few times, though I was not at a startup but rather contacting them re a topic of mutual interest. One was a VP at a top-5 biotech fund and another the former head of a well known VC who was doing angel investing in between jobs. The former connected me with a bunch of his VC friends at other firms, relationships I still have. The latter, in his reply to my cold email, invited me to his home to check out his (rather impressive) home brewery setup Playing the student card works, as does contacting them regarding something that they're interested in / that benefits them