The title says it all. Who were the species that the Vulcans first met? I'd prefer canonical answers but I'll accept things from books or other media that aren't exactly canon.
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A complex question, and one that's not easy to answer. Not only did the Vulcans have at least two flourishing periods in pre-history, but they also had at least two dark ages where they lost, and then slowly regained, the capacity of going to space, along with any records of having done so.
Essentially, the Vulcan civilisation has been aware of aliens for as long as they've had a written language, and well before the present 'Age of Reason'.
The first alien species encountered by the Vulcans were the Furies. They visited (and dominated) a primitive Vulcan civilisation around 3-5000BC and were contemporaries of the Unclean. Note that they were also one of humanity's first contact with aliens, predating the Greek gods like Apollo by more than 2000 years.
“The hatred you feel deep inside is genetic, Jean-Luc.” She was looking at him now, her dark eyes filled with compassion. He wasn’t certain he wanted to see that. “The Furies terrorized your people thousands of years ago. And not just your people. The Vulcans, the Klingons, even the Ferengi fell prey to them.”
Picard nodded. “I know.”
Guinan went on. “But do you really, Jean-Luc?” She gave him a look and he wondered if he really did have any understanding.
“After a millennium of rule in this sector, something arrived and overthrew the Furies. The Klingons called them the Havoc.”
She stood upright, looking into his eyes. “The Vulcans wrote only of the terror that ensued in the battle. Humans, on the other hand, had several reactions to their protectors. The ancient Greeks made them into gods, Moors and the ancient pagans agreed with the Klingons. Their graphic representations of these ‘saviors’ was grotesque. Over time they became stylized in garden statuary.”
Officially, the first contact had with another non-godlike race was with Orion pirates, some 50 years after Surak's birth.
It was around the time of Surak's birth, when the FireEye's light reached Vulcan, that the first electromagnetic signals from Vulcan reached Etosha in their turn, and notice was taken.
Their first contacts with the Orion pirates, forty-five years later, would have been enough to disillusion even a Terran steeped in all old Earth's legends of bug-eyed monsters intent on stealing their women and subjugating their planet. The Vulcans had no such legends: they expected to deal with strangers hospitably, and courteously, though always from strength. They had no idea that their strengths were in areas that would mean nothing to the Duthulhiv pirates who first reached them.
But we now know from comics like Star Trek: Strange New Worlds - Illyrian Enigma that pre-Surak Vulcans were busily contacting alien races aplenty, as well as seeding colony worlds, to the point that meeting the Illyrians wasn't even considered an especially memorable experience. These records were evidently lost during the various wars fought by the Vulcans amongst themselves.
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