My first LJ friend was thomryng, who gave me a sign-up code back in those last days of needing to have one to join. We met when we were both temping at FormerMyCo and discovered a mutual passion for ancient religions -- not something one usually finds in the course of an office job.
He is indeed still on my friends list.
My sister, who no longer has an active journal, was my second friend. She was living across the country and at that time was doing more posting to LJ than she was keeping up with family through direct contact. I figured LJ was the best way to keep tabs on her. I never expected to become so deeply involved in an actual community.
The other earliest friends who are still around are queenofhalves and mamadar and gothic_coop