It's just an LED. No need to baby it!
Split the series resistor in half. Make the first half really big (pulse rated, preferably a larger size, maybe as big as a wirewound power resistor). Put a TVS in the middle, or maybe even an MOV.
This gets a survivable LED and TVS, but the front resistor may not handle it. If it blows out instantly, the circuit's dead either way. Current limiting would be nice.
Consider using a PTC for the first resistor. These are available in ceramic types that handle much more voltage than the polymer fuse types. It's possible that it can heat up and partially open the circuit before the TVS or PTC fails.
Note that you can offset some of the PTC's voltage drop by choosing a higher TVS rating. If your resistors are sized for nominal, 20mA or whatever, at 5V, then the LED is straining at maybe 20-30V (~100mA). Not that that's much savings out of a 230VAC supply, but 10% isn't nothing.
To get really fancy, you might consider a current limiter using depletion mode MOSFETs like DN3545 or LND150; there is a two-transistor connection that allows bidirectional current limiting with one resistor to set the current. Then you can use a bigger MOV at the front end to protect against not only unreasonable voltages like mains, but surge as well. (In this case, you could remove the inside TVS and series resistor, and use an antiparallel diode (say 1N4148) across the LED to protect it against reverse voltage. The MOSFETs will limit current to a ~fixed value, from just a few volts all the way up to their rating.)
The last option of course is the most expensive, but also the most reliable. Shop around.
Tim