I use port 465 all the time.
The answer by danorton is outdated. As he and Wikipedia say, port 465 was initially planned for the SMTPS encryption and quickly deprecated 15 years ago. But a lot of ISPs are still using port 465, especially to be in compliance with the current recommendations of RFC 8314, which encourages the use of implicit TLS instead of the use of the STARTTLS command with port 587. (See section 3.3). Using port 465 is the only way to begin an implicitly secure session with an SMTP server that is acting as a mail submission agent (MSA).
Basically, what RFC 8314 recommends is that cleartext email exchanges be abandoned and that all three common IETF mail protocols be used only in implicit TLS sessions for consistency when possible. The recommended secure ports, then, are 465, 993, and 995 for SMTPS, IMAP4S, and POP3S, respectively.
Although RFC 8314 certainly allows the continued use of explicit TLS with port 587 and the STARTTLS command, doing so opens up the mail user agent (MUA, the mail client) to a downgrade attack where a man-in-the-middle intercepts the STARTTLS request to upgrade to TLS security but denies it, thus forcing the session to remain in cleartext.