I had a hard time finding the Treo technical reference guide (which used to be downloadable from Handspring's web site), so when I finally found it I put a copy of it on my web server, here:
http://www.burtonsys.com/handspring_treo_techref.html
The TechRef is circa 2002, and it covers the Treo 90/180/180g/270. It doesn't cover the Treo 300, but the 300 is very similar to the 270 (but PCS/CDMA instead of GSM), and the pinouts are identical (see p.50 of the TechRef).
Note that the Treo's serial lines are TTL (5v) levels, not RS-232. If you need RS-232 levels then the easiest solution is to buy a Treo serial hotsync cable on eBay.
I hacked up a serial hotsync cable to make this connector:
http://www.burtonsys.com/treo_connector.jpg
The red wire is RxD.
The orange wire is TxD.
The black wire is ground.
The circuitry that you see on the little PCB is the TTL/RS-232 voltage level conversion circuit that hides in the connector housing of a serial hotsync cable. That big silver thing in the middle is the hotsync push-button (which should tell you which side of the connector we're looking at in the photo).
For my application I didn't need the RS-232 level translation, so I just cut the traces and used wires soldered directly to the edge connector. (Soldering those tiny connections is challenging, BTW!)
-Dave
dave314 at burtonsys.com