We're arriving at Geneve Airport on 1 Jun 1345 ETA. We're planning to head straight to Zermatt. Is it necessary for us to book the train tickets prior to arrival? Or it is ok to purchase the tickets when we're at the Airport?

Is it necessary for us to book the train tickets prior to arrival?
No.
Or it is ok to purchase the tickets when we're at the Airport?
Yes.

Thanks for the reply. Will 3 nights in Zermatt excessive considering my ETA to Zermatt will be late in the evening for the 1st night?

If I understand correctly, you want to know when you're arriving in Zermatt after connecting by train from Geneva. There are seven (7!) possible connections on June 1 after your ETA (for non-airliners: ETA = Estimated Time of Arrival), the earliest possible one (however a little tight) leaving at 14:27 (arriving 18:14) and the latest possible one leaving at 19:47 (arriving at 23:44). For your personal schedule as well as ticket prices, click here. Three nights in Zermatt are by far not excessive - you could easily spend one or two weeks and still not have done all the attractions this Swiss gem has to offer.

Many thanks. Actually I'm from Singapore and planning a holiday to Swiss from 1 Jun to 16 Jun. My itenaries are free. I've been to Swiss in Dec 09 and visited Appenzeller Land, Luzern, Interaken (unfortunately trip up to the top was not done due to bad weather) and Mt Rigi (lovely place for hiking). I'm travelling with my wife n daughter and we moved around with rented car.
Any good recommdation for this time round? I'm thinking of Montreux, La Gruyere, Berne, Thun, Zermatt and some french land like Yvoire and Chamonix.

Hi again. Had I known that you fly in from Singapore and that you have two weeks in Switzerland (please don't use Swiss+, this is the name of the national air carrier), I would have adviced differently. Considering what you already have seen, I suggest to do the +Southern Loop of Switzerland:
Start with one night in Montreux. Reason: You'll be jet-lagged, overnighting in Zermatt right after arrival might result in not being able to sleep due to its altitude - something people living at sea level are not aware of.
Then do Montreux - Zermatt. Go up to Gornergrat and Kleinmatterhorn. If you have seen these, you won't need to see Jungfraujoch anymore. Hike.
Zermatt - Brig - Simplon pass (by postal coach) - Domodossola - (Centovalli) - Locarno. This is Switzerland's Florida.
Locarno - Lugano - Sondrio - Bernina Express - St. Moritz. Hike, hike, hike...
St. Moritz - Zurich. Overnight or go on to Berne, Switzerland's capital.
Berne - Thun - Spiez - Zweisimmen - Montreux (Golden Pass Route) - Lausanne - Geneva.
This takes some careful planning, it's however going to be something that you won't forget so quickly. All can be done by public transport, a car is definitely of no use for this itinerary. You may think about buying a travel pass which makes travelling a bit less expensive.
Forget about France, it's too much, too complicated to be added here. Come back later :-)
You can easily visit Gruyeres medieval town/castle cheese diary anc Broc chocolate works Thursday June 2nd as a day trip from Montreux, either individually (requires some planning, because of the different openign hours of the sites and the local transport between Broc and Gruyeres) or as an organized trip by panoramic train: http://www.goldenpass.ch/CMS/default.asp?ID=414

tyongchi: Sure enough could you do the Chocolate Train as neckervd suggested. To understand slightly better, here is the link to the English language contents of the suggested website. BTW: The mountain behind Gruyères is not called Toblerone :-) If you get my joke...?

So many places to go but yet so little time. Lol, I've reviewed my itinerary (for the first half) and appreciate your comment.
1 Jun - Arrival at Geneva and head straight to Zermatt. ETA at Zermatt around 1900 hrs. Stay in Zermatt for 3 nights.
4 Jun - Head for St. Moritz via Glacier Express. ETA around 1800 hrs. Stay 2 nights (or is 1 night sufficient?)
6 Jun - Head for Tirano via Bernina Express. Stay 2 nights (or is 1 night sufficient?)
8 Jun - Head for Chur via Bernian Express again. Stay 2 nights in Chur.
10 Jun ..... not decided yet. I'm thinking of picking up a car and do the rest of the trip on wheels. Places include Bern, Montreux, Gruyeres.
I'll probably get the Swiss Flexi Saver pass.
Thanks again for your advice.

Why backtracking? Additionally, there is nothing to be seen in Tirano or Chur. The route I gave you above is avoiding exactly this, you leave out the spectacular train ride acrross lovely Centovalli (= hundred valleys). Please don't rent a car, you'll have plenty of hassle parking it in Berne and Montreux.