The TVS is already a zener, so there's no need to use extra.

DC overvoltage depends on source impedance. Some surges can be clamped, or even bypassed (ESD, EFT, even 8/20us induced surge to some extent), others are difficult or impossible to clamp (automotive load dump, crossed wiring overvoltage). You may need to ride through or disconnect the overvoltage, instead.
Note that polyfuses take quite a long time to open, 100s ms -- in this time the TVS will have cooked off. They used to make three-terminal paired parts, where the TVS heats the poly-goo making it open quickly and safely on overvoltage, but they're pretty much unavailable these days AFAIK. Alas. You may instead need an electric fuse or current limiter, or some other circuitry to handle it. Or a good old fashioned crowbar, with a big enough SCR to handle clearing current of the fuse.
Also, note that polyfuses have maximum current and voltage ratings; current may be easily exceeded even well within voltage ratings. Check the internal resistance, and add more if necessary. Yes, this will reduce the efficiency of your system; such is the price for safe operation, and a hint that a more elaborate method (as above) may be desirable.
Tim