Since Jiraiya does not start out in sage mode, and Killer Bee does not start in bijuu mode this fight will mirror MS Sasuke vs Bee somewhat.
Jiraiya knows to avoid Killer Bee's taijutsu since he's a taijutsu king. Jiraiya can easily summon and lather Killer Bee in oil, which then he proceeds to use fire style on Killer Bee. BUT WAIT! Killer Bee has now entered V2 Hachibi.
V2 Hachibi lariats Jiraiya and he dies :'(.
If Jiraiya barely suppressed a 4 tailed Naruto, I have my doubts about him defeating v2 hachibi.