I just did this very thing. I was tasked with getting our existing 32 Bit 2000 Production Cluster up to SQL Server 2005 64 bit. I was given very little time to prepare, no environment to test in, a 3 day maintenance window and very little chance of success. 
The thing is, not only can you not mix 32 and 64 in a cluster but, you
have to have both nodes up and the cluster configured to do a SQL server
2005 cluster install. Well, you don't HAVE to I suppose but, it's not the MS supported method.
I succeeded it took approximately 2.5 days, I took my time and got sleep. You might be able to do it sooner. I would also set management's expectation level for one of utter and complete total failure if you are given lack of time to prepare and test as I was. Below is my experience and the general steps involved.
Prep: Read The SQL Server 2005 Upgrade Handbook, SQL Server 2005 Security Best Practices - Operational and Administrative Tasks, and most importantly SQL Server 2005 Failover Clustering White Paper. Run SQL Server 2005 Upgrade Advisor Make note of the results, deal with the things it tells you too.
One the day of your upgrade:
1) Say a little Prayer
2) Make Backups of your databases and servers.
3) Extract SQL Accounts
4) Migrate DTS Packages (in My case) from 2000 to 2005 instance on a Laptop using SQL 2005 developer Edition and the DTS Migration Wizard.
5) Extract SQL Agent Jobs
6) Make notes of or extract DDL for DB Links, ODBC Sources, Etc. You can extract ODBC Sources by exporting the registry key HKEY_LOCAL_MACHINE\SOFTWARE\ODBC\ODBC.INI
7) Detach The databases (ones that will be migrated).
8) Take a Deep Breath.
9) Shut Down your existing Cluster
10) Blow away existing cluster and install Windows 2003 x64. Apply SP2, get Updates, Update firmware and drivers for hardware.
11) Create and test your cluster.
11a) Make sure your Heartbeat is setup correctly.
12) Install SQL Server 2005 x64 on your Cluster, Make sure you also install things like SSIS and MS to the inactive node also, they aren't done for you.
13) apply SP2
14) Attach Databases
15) Restore Accounts, ODBC, Jobs, Links, etc.
16) Use Package Migration wizard to move packages over from were they were put earlier.
17) ReIndex and Update Statistics.
That was about the gist of it. The cluster just had it's first week of full production load and is doing very well. Yes, there is a noticeable difference I have seen in watching perfmon. CPU is lower, I/O is a tad Faster, page file usage is at 0%, cahe hit ratio at 99%+.
Good Luck. 