The 49-year-old, who worked with the Chelsea interim boss for a year as managing director of the Reds, believes the Spaniard was never suited to the Stamford Bridge post
Purslow worked alongside Benitez for a year at Anfield before the Spaniard left the club by mutual consent in 2010 and subsequently blamed the 49-year-old for forcing him out.
And, after Benitez hit the headlines last week for his post-match press conference following the FA Cup victory over Middlesbrough, Purslow has questioned the spontaneous nature of the outburst.
"This wasn't a rant," Purslow told BBC Radio 5 Live. "It was a planned outburst, as Rafa plans everything.
"The piece about his title [of interim manager] was managed - I expect a quiet word was had the next morning that it doesn't look good criticising your employment.
"He does have form in the media in terms of outbursts at employers, particularly Valencia, Liverpool, [Inter] Milan. He probably cares about these things too much, and focuses on them too much."
Purslow also expressed his belief that Benitez was never suited to the Chelsea job due to the lack of power he would be afforded by Roman Abramovich.
"It doesn't suit Rafa's book," he explained.
"There was a very dysfunctional ownership structure at Liverpool for that period which gave him disproportionate power, perhaps the most powerful contract in professional football for a manager, a contract that gave him much greater power than the normal manager.
"So I've got to say that when I saw him taking this job, going to a club where the reverse is true, on a temporary basis, no role in transfers, no total control, there wasn't a fit."