Sessions are as secure as the network and your server, but you need to understand how they work.
Session data is stored on the server, by default in files. If your server access is shared, then the data may be readable by others.
The session key (session ID) is transmitted on the wire in cleartext, as a cookie or as a part of the URL.
If the network is not secure, and you're not running all of this over an encrypted connection, then theoretically a session can be hijacked by a "man in the middle." Unlikely but possible.
Session IDs are not predictable, not sequential, and in a practical sense not guessable.