In your 14 gallon you don't have room for any more fish (but I assume you knew that already) so we must be talking about fish for the 20 gallon.
If you didn't have those black widows (because they have a tendency to nip), I'd have suggested getting a single male pearl gourami. However, as you
do have those widows, perhaps consider a single male banded gourami (
Colisa fasciata). These grow to 4" and are similar to dwarf gouramies in appearance but much hardier and (IMO) somewhat prettier as well.
Here are some pics:
http
/www.akwafoto.pl/konkurs/konkurs03/fotki141_150.htm (4th and 5th pic down - ignore the honey gourami just above the banded in the 5th pic

)
http
/www.igl-home.de/bilder/fasciata.jpg
http
/membres.lycos.fr/aqua5/aquariophili...sa_fasciata.php
http
/www.akvariumas.lt/zuvys/belontiidae...asciata_big.jpg (female below - males are brighter and have logner and more pointed dorsal and anal fins. Also, females are 'stockier', deeper-bodied and wider when viewed from above. Males will eventualy turn out larger than females but this, obviously, isn't a reliable way of sexing them as juveniles.).
I see you've used the term 'black widow' (as oppsoed to 'black skirt') so I expect you live in the UK - I've seen
Colisa fasciata quite often here - even in places like pets at home. Be careful though - they are not always labelled correctly
Depending on exactly what type of molly you have, you may also have room for a couple of female bandeds. However, as the potential size of your average molly is impossible to predict, I'd leave that option out for the time being.
Croaking gouramies are another species you could keep - a trio would be ideal (1 male, 2 females). These may nto be quite the kind of fish you were after though.
Concerning bolivian rams - a pair would work but would be quite aggressive when breeding. German blue/gold rams are equaly suited to your setup and less aggressive but are somewhat less hardy and more likely to get picked on (when not breeding

).
You may want to look into obtaining a trio (1 male, 2 females) of american-flag fish (a killifish) as an alternative to both cichldis and gouramies:
http
/www.aqualandpetsplus.com/Oddbal1182.jpg
They are easy to breed compaired to gouramies but less aggressive towards nonconspecifics than bolivians. Males are especialy brightly colored whereas females are a bit duller and smaller in size.