Technically, no. Depending on how literal you interpret the term "seat", this will either be the second time or the premise of the question is wrong, since there are, in fact, enough seats.
So, it will be either the second or "zeroth" time, but not the first.
tl;dr
In some sense it has happened before that an astronaut had no seat in a lifeboat available, but in another sense, it is actually not true that Butch and Suni don't have seats available.
Soyuz MS-22
There was an interesting situation in 2023 where the lifeboat rules were tested: the Soyuz MS-22 capsule had sprung a leak in its coolant system, and there was concern that the astronauts would be subjected to high temperatures during the return flight. Therefore, it was decided to push the Soyuz MS-23 mission forward and turn it into an uncrewed mission.
However, this meant that cosmonauts Sergey Prokopyev and Dmitry Petelin, and astronaut Frank Rubio would have had no lifeboat for two months until the arrival of Soyuz MS-23.
NASA decided that Frank Rubio's seat liner would be un-installed from Soyuz MS-22 and jerry-rigged into Crew-5's capsule Endurance. While Crew Dragon always flies with a crew of at most 4, it was originally designed for 7, therefore, its environmental control and life-support systems would easily be able to handle a crew of 5; this also means there is enough space on the cargo pallet behind the four seats, where the other three seats would have been. Crew Dragon's water landing is fairly benign, so not having a proper seat for Frank Rubio was deemed acceptable – remember, we are only talking about an emergency return, where different Flight Rules apply and NASA is willing to accept more risk.
Roskosmos decided that Soyuz MS-22 was probably safe enough for an emergency return, especially with the reduced heat load of only 2 cosmonauts, so it served as lifeboat for Sergey Prokopyev and Dmitry Petelin.
In the end, none of that was needed. After the arrival of Soyuz MS-23, the three seat liners were moved from Endurance and Soyuz MS-22 to Soyuz MS-23, at which point, the normal lifeboat situation was re-established.
Soyuz MS-22 returned uncrewed. To make its return as easy and fast as possible, the ISS was pitched 90° and the Soyuz's thrusters were fired longer than normal, reducing the return journey to only 55 minutes. The temperature reached 50°C, which was lower than the worst-case estimates, and would have been survivable.
Starliner
NASA already did all the relevant studies back in 2023. So, they know that they can, if needed, use the cargo pallet of Crew Dragon to transport additional astronauts. The major difference between the MS-22 situation and now, is that Frank Rubio had a Sokol flight suit and a Soyuz seat liner whereas Butch Wilmore and Suni Williams have Boeing flight suits. If I understood Steve Stich correctly during the press conference, there is already a spare SpaceX Crew Dragon flight suit on the ISS which fits at least one of the two astronauts. However, I believe there are no additional umbilical ports except those in the armrests of the seats, so there would be no way to connect the suit to the environmental control and communications systems.
In addition, NASA has already cleared Starliner for use in an emergency back in June.
So, while Starliner is still docked to the ISS, it can serve as a lifeboat for Butch and Suni. After it undocks, Crew-8's Crew Dragon Endurance will serve as the lifeboat.
Technically, Butch and Suni will indeed not have "seats" in the literal sense of the word. But they will have a place to shelter and an emergency return vehicle, so they will have "seats" in the metaphorical sense of the word.
Why is Starliner both safe and unsafe?
It may be a bit confusing why Starliner is deemed unsafe for a return flight, but safe for an emergency return flight. The reason is that the two situations have different risk assessments:
- In an emergency situation, the choice is between almost certain death on the ISS vs. the relatively small possibility that the thrusters fail during the reentry sequence.
- In the nominal situation, the choice is between a slightly uncomfortable ride vs. the possibility that the thrusters fail during the reentry sequence.
The press conference
There is a lot of in-depth information in the press conference, most of it in language that can be understood by an interested amateur:
NASA’s Boeing Crew Flight Test Status News Conference