So, firstly enable NetFlow like you would on any other IOS switch. It’s worth noting that at some point during the configuration you’ll likely get one of those trademark heart-stopping console freezes for up to 20 seconds. It’s not clear if this actually interrupts switching.

switch(config)#interface Te2/2
switch(config-if)#ip flow ingress
switch(config-if)#ip flow egress

I understand that this command used to be called ip route-cache flow, just to add to the confusion.

Now enable NDE to export your data to something like flow-tools:

switch(config)#ip flow-export source Vlan1
switch(config)#ip flow-export version 5 origin-as # This is where it hangs a while...
switch(config)#ip flow-export destination x.x.x.x yyyy

At this point you can run sh ip flow export to see your many flows being exported. Well, except you can’t, because on the 6500, the ip flow class of commands only deal with NetFlow for packets which hit the supervisor module, i.e. forwarding cache misses. (Older cat6500 hardware would merit a discussion of MSFCs and PFCs here, but my hardware isn’t old, so we don’t need that complication.)

So, to enable NetFlow and NDE for dCEF switched packets throughout the switch, the appropriate incantations are done using the mls series of commands:

switch(config)#mls netflow
switch(config)#mls nde sender version 5
switch(config)#mls flow ip interface-full

Confusingly, although it uses the NDE collector you configured earlier, you must view the MLS NDE stats differenlty, by using sh mls nde.

More detail can be found in the Configuring Netflow section of the Catalyst 6500 config guide.