I'm putting a panel in the garage with a 200A breaker on it fed by this cable. On it will be two HPWCs with 100A breakers, and a 14-50 for backup. Are you saying this violates code?
I have another 14-50 for the volt, but that's staying on the other panel which is served by a different feeder.
If you anticipate that both HPWC's may be used at the same time, then yes it does violate code.
Now, some electricians will "cheat", because they argue that as the current never exceeds 80A per HPWC, it's ok to skimp on the feeder. However, there's nothing in the code that gives that flexibility in the install. This is the same case where some electricians will argue that #2 NM cable is sufficient for a 100A HPWC install - they argue that the combination of the 25% overhead for continuous loads combined with the fact that the conductors in NM cable are really rated at 90 degrees, not the 60 degrees the code requires, means they can use a 95A-rated cable to serve a calculated load of 100A. Some inspectors may allow it to slide by, but the inspectors I've asked said they would fail it because nothing in the code gives them that flexibility. Your best bet is to contact your local permitting office and ask them if they will accept it.
There is a rule that permits a 75% demand factor for 4 appliances that are fastened in place, but you don't have 4 HPWC's here, so you can't rely upon that.
The way you determine this is pretty simple...
First, start by calculating your load. If you expect to be using both HPWC's and want the 14-50 to be backup (meaning, non-concurrent), then you'll require 160A of continuous load.
215.2(A)(1) says that you calculate the load per 220 parts III/IV/V.
220.40 says "the calculated load of a feeder or service shall not be less than the sum of the loads on the branch circuits supplied., as determined by part II of this article, after any applicable demand factors permitted". There are no demand factors that apply to 2 HPWC's in this case, and we'll take advantage of the 220.60 non-concurrent loads rule for the 14-50.
So, back to 215.2(A)(1)(a)... "where a feeder supplies continuous loads or any combination of continuous and noncontinuous loads, the minimum feeder conductor size shall have an allowable ampacity not less than the noncontinuous load plus 125 percent of the continuous load". 160 x 1.25 = 200A, so the minimum feeder conductor size shall not be rated at less than 200A.
310.15(B)(16) is the table that shows maximum allowable ampacities of conductors. The 4/0 conductors you use are going to be rated at 90 degrees, but you almost always use 75 degC columns because it's extremely rare that you find residential equipment rated for 90 degC termination. Therefore, the conductors are good to 180A. Because your calculated load is 200A, you can't use this cable for these loads. Red flag #1...
Now, there's also another twist in here: You're using a cable assembly. When you use NM or SER, there are special rules. If that SER cable runs in a space with thermal insulation, 338.10(B)(4)(a) states that "where installed in thermal insulation the ampacity shall be in accordance with the 60 degC conductor temperature rating", which is 150A. As many garage walls and attics are insulated, this tends to be the case in many installations. (As a side note, NM or "Romex" must *always* take the 60 degree C column in its rating, per 334.80). Red flag #2...
I would recommend contacting your inspector and asking if they would permit that. Be sure you tell them you're offering an 80A *continuous* load when you ask the question. I've seen a lot of inspectors fail to consider the EV load as continuous.
Personally, I would run PVC and consider either AL 250 mcm / CU 3/0, or run parallel conduits with parallel conductors, since above 1/0 you can parallel them per 310.10(H).