I have a similar problem.

~$ openssl s_client -connect imap.ufvjm.edu.br:993
CONNECTED(00000003)
depth=2 C = IL, O = StartCom Ltd., OU = Secure Digital Certificate Signing, CN
= StartCom Certification Authority
verify error:num=19:self signed certificate in certificate chain
---
Certificate chain
 0 s:/C=BR/CN=imap.ufvjm.edu.br
   i:/C=IL/O=StartCom Ltd./OU=StartCom Certification Authority/CN=StartCom
Class 1 DV Server CA
 1 s:/C=IL/O=StartCom Ltd./OU=StartCom Certification Authority/CN=StartCom
Class 1 DV Server CA
   i:/C=IL/O=StartCom Ltd./OU=Secure Digital Certificate Signing/CN=StartCom
Certification Authority
 2 s:/C=IL/O=StartCom Ltd./OU=Secure Digital Certificate Signing/CN=StartCom
Certification Authority
   i:/C=IL/O=StartCom Ltd./OU=Secure Digital Certificate Signing/CN=StartCom
Certification Authority
---
Server certificate
-----BEGIN CERTIFICATE-----
snip
-----END CERTIFICATE-----
subject=/C=BR/CN=imap.ufvjm.edu.br
issuer=/C=IL/O=StartCom Ltd./OU=StartCom Certification Authority/CN=StartCom
Class 1 DV Server CA
---
No client certificate CA names sent
Peer signing digest: SHA512
Server Temp Key: ECDH, P-256, 256 bits
---
SSL handshake has read 5723 bytes and written 326 bytes
Verification error: self signed certificate in certificate chain

snip

Start Time: 1496262567
Timeout   : 7200 (sec)
Verify return code: 19 (self signed certificate in certificate chain)
Extended master secret: no

offlineimap returns

ERROR: Unknown SSL protocol connecting to host 'imap.ufvjm.edu.br' for
repository 'XXXXX-Remote'. OpenSSL responded:
[SSL: CERTIFICATE_VERIFY_FAILED] certificate verify failed (_ssl.c:661)

Please, have you any clue here?

Thankx!

-- 
Marcelo

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