I'm not sure anyone can tell ... except for another puffer.
Some of our reef fish are sexually dimorphic (males and females look different), but the great majority aren't, and males and females are indistinguishable to our eyes.
Whilst Maritimer's advice is true for most puffers I do believe that there is "believed" to be some sexual dimorphism in valentini.
If you look at the picture above you will see what is attributed as a male, with blue lines running behind it's eye and grey short lines on the underside of its chin. You will see the absence of these in the smaller fish which is believed to be a female. I don't know if this is a maturity thing and only adult males get this colouration or if young males have it to.