Can new Navigo Decouverte Card be purchased at CDG?

Navigo cards can be purchased at CDG. The ticket office is close to the train (fRER) station. Best advice for this is to take a passport size photo with you. The photo kiosk there is difficult to use

Seconding Glenda. If you have the photos, it is fast and easy at the CDG RER
station.

The new Navigo Decouverte (physical) Card (costs €5 good for 10 years) and Navigo Pass can be purchased from the ticket office at the CDG T2 TVG (& RER) train station. Make sure they bring along a face photo (3cm x 2.5cm) as the card requires a photo and their name written on it. The Navigo weekly pass for all-zone (1-5) now cost €30.

P.S. those train ticket machines do not sell the Navigo Decouverte physical card; they have to buy it from the ticket office.

Direction to the CDG Terminal 2 TVG train station and ticket office (BILLETS PARIS ET ÎLE-DE-FRANCE):

https://parisbytrain.com/paris-airport-terminal-2-train-photo-tour/

I have recently read reports elsewhere that new arrivals hoping to get their ND at CDG have found long lines or no staffed Service Desks. So the friends need to have a Plan B in case either occurs. Of course busyness may also depend on when they are going.

There are two sales windows at CDG where you may purchase Navigo cards and fares; one at Roissypôle serving terminals 1 & 3 (on the free CDGVAL line), and a second in terminal 2. If one has long lines, go to the other. The windows are staffed whenever the trains are running.

The RER B to Paris serves both stations.

Claire is right and Tocard’s advice is very good. The line at Terminal 2 for a real person at the window can easily take over an hour. I waited in it for over 30 min once, and left because only 2 people had been served in that time and there were at least 10 people in front of me. I was severely jet-lagged, had been up for over 30 hrs and waiting in that line was excruciating. A Plan B is always a good thing.
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What day do your friends arrive? Remember that a weekly pass for the current week (Monday through Sunday) can only be purchased until Thursday at midnight. So if they arrive Friday, Saturday or Sunday and intend to use the RER to reach central Paris, their is no point in standing in line at CDG to get the card holder. They would be better off getting an RER ticket at one of the kiosks and then sorting out the Navigo pass once they’re in the city at a manned Metro station.

I was in Paris in May and bought a Navigo Easy card. This card does not require a photo, you can buy it at a Metro station, and it can be topped up with trips anytime. It's not for permanent residents or frequent visitors but works just great! Highly recommend.

the Navigo Easy is great but it is not at all the same as the Decouverte. You cannot load the weekly pass for zones 1-5 on the Easy -- it is basically for Paris transport. The ND gives you the whole Ile de France including CDG

And the Easy card is essentially individual tickets which are more expensive than a Navigo Découverte if you plan to use a fair amount of public transportation. .

The Navigo Easy card accepts any of the following:

Tickets t+; 2.10€ each/10 for 16.90€; 8.45€ in groups of 10 for children 4 to 9

Roissybus 14.15€

Orlybus 10.05€

Day pass; Zone 1-2 fare: 8.45€, Zone 1-5 fare: 20.10€.

Jeune week-end pass; day pass for those under 26. Zone 1-3 fare, 4.60€; Zone 1-5 fare, 10.10€

I believe ParisbyTrain.com explains all the Passes very well and might be helpful for you.