I'd really recommend it - it's the first sci-fi series that worked to a planned story arc, paving the way for a lot of the stuff we watch today, like GoT...
First season is a bit slow, but it lays all the groundwork. But once it picks up right at the end of S1, you'll be swept away, I promise. Seasons 3 and 4 are real gems. OK, the sets are a bit ropey (the pilot aired in 1993 after all) but the writing is amazing and the acting is unique.
Joe Straczynski used a lot of theatre actors rather than sticking to those who only did TV. You get cameos from John Vickery, John Schuck, Jane Carr and even Guy Siner (he of Lt Gruber fame)...
I got introduced to B5 first time round by some friends at uni - I was a trekkie and didn't "get" it at first, but the episode "Confessions and Lamentations" really blew my mind, and I've been hooked ever since.