Molyneaux, 38, says it'll be nice not to worry about the 'stresses and strains of management or any staff responsibilities' while at the PMC Stadium.
The former Oxford United, Forest Green and Hawks defender has been out of the game since both he and Catlin were relieved of their duties at Portchester last October.
Prior to that, Molyneaux stepped down from his role as Gosport manager last summer after a season in charge at Privett Park as he was unable to dedicate the time required to the position.
Yet, despite making moves into management in the past few seasons, he still trained with the first team while Boro manager and also mixed assistant managerial responsibilities with playing during his brief Portchester spell. He made four league and cup starts for the Royals in 2020/21, plus three off the bench.
And Molyneaux is in no doubt he'll be able to have an impact on and off the pitch at Baffins.
He said: 'I didn’t really want a hard stop when I left Havant, so I played for Gosport in their reserves and I trained most sessions because I was fortunate enough to have Kev Braybrook as a coach, so I still trained even when I was Gosport manager.
‘I then joined AFC Portchester as assistant manager and played a fair few games as well.
‘In terms of not being part of any staff and just going back to being a player, it’s a big thing.
‘It’s not like it’s been a hard stop and I haven’t played for two years. I feel in good shape, I feel ready and I’m excited to get back playing, without the stresses and strains of management or any staff responsibilities and just concentrate purely on playing.'
But Molyneaux is more than willing to help out from a coaching perspective should he be asked by Baffins boss Shaun Wikinson, who is only a year older than him.
He is joining a young squad and wants to offer his services in any way he can as the most experienced head in the playing squad.
Molyneaux insisted: 'Never say never, we’ll see how it goes (coaching at Baffins).
‘I certainly don’t want to go in as a coach, I want to go in as a player; whether they want me to coach I don’t know, but we’ll see.
‘There’s a really good youthful team (at Baffins) but it is lacking some experience, so whether it’s on the pitch or off the pitch, I think where I’ll contribute is from an experience standpoint.
‘They need it (experience), they’ve got a really good team, but without direction on the pitch it’s not ideal.'