I've used Sybase in the past, though not with PHP, and these days I'm using MS SQL Server (which is Sybase' twin brother, separated at birth years ago) with PHP. I use ODBC to access it, so I would exepect the same code to work fine under both DBMS.
Only problem I had so far was with getting result sets from stored procedures - I saw on this forum that this was not supported yet in PHP. It may be different if you use the Sybase-specific functions, but I haven't looked into these functions for obvious reasons.
Hope this helps
Yaron Yogev