Cowbay via Postfix-users:
> So, I will collect necessary information next time I encounter this 
> issue as what Viktor suggested.

Please note that Postfix does not automatically use the "system"
root CA store that openssl s_client and curl may use. That could
result in verification differences between Postfix and other tools.

https://www.postfix.org/postconf.5.html#tls_append_default_CA

tls_append_default_CA (default: no)
    Append the system-supplied default Certification Authority
    certificates to the ones specified with *_tls_CApath or
    *_tls_CAfile. The default is "no"; this prevents Postfix from
    trusting third-party certificates and giving them relay permission
    with permit_tls_all_clientcerts.

        Wietse
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