I can reproduce this, and it seems to stem from the openssl version used (0.9.8l). Running openssl s_client -connect grooveshark.com:443 with 0.9.8l gives

CONNECTED(00000003)
depth=3 /L=ValiCert Validation Network/O=ValiCert, Inc./OU=ValiCert Class 2 Policy Validation Authority/CN=http://www.valicert.com//emailAddress=info@valicert.com
verify error:num=19:self signed certificate in certificate chain
verify return:0
22456:error:0407006A:rsa routines:RSA_padding_check_PKCS1_type_1:block type is not 01:rsa_pk1.c:100:
22456:error:04067072:rsa routines:RSA_EAY_PUBLIC_DECRYPT:padding check failed:rsa_eay.c:697:
22456:error:1408D07B:SSL routines:SSL3_GET_KEY_EXCHANGE:bad signature:s3_clnt.c:1448:

With 1.0.1c, it gives


CONNECTED(00000003)
depth=3 L = ValiCert Validation Network, O = "ValiCert, Inc.", OU = ValiCert Class 2 Policy Validation Authority, CN = http://www.valicert.com/, emailAddress = info@valicert.com
verify error:num=19:self signed certificate in certificate chain
verify return:0
---
Certificate chain
 0 s:/C=US/ST=FL/L=Gainesville/O=Grooveshark/CN=*.grooveshark.com
   i:/C=US/ST=Arizona/L=Scottsdale/O=GoDaddy.com, Inc./OU=http://certificates.godaddy.com/repository/CN=Go Daddy Secure Certification Authority/serialNumber=07969287
 1 s:/C=US/ST=Arizona/L=Scottsdale/O=GoDaddy.com, Inc./OU=http://certificates.godaddy.com/repository/CN=Go Daddy Secure Certification Authority/serialNumber=07969287
   i:/C=US/O=The Go Daddy Group, Inc./OU=Go Daddy Class 2 Certification Authority
 2 s:/C=US/O=The Go Daddy Group, Inc./OU=Go Daddy Class 2 Certification Authority
   i:/L=ValiCert Validation Network/O=ValiCert, Inc./OU=ValiCert Class 2 Policy Validation Authority/CN=http://www.valicert.com//emailAddress=info@valicert.com
 3 s:/L=ValiCert Validation Network/O=ValiCert, Inc./OU=ValiCert Class 2 Policy Validation Authority/CN=http://www.valicert.com//emailAddress=info@valicert.com
   i:/L=ValiCert Validation Network/O=ValiCert, Inc./OU=ValiCert Class 2 Policy Validation Authority/CN=http://www.valicert.com//emailAddress=info@valicert.com
---
Server certificate
...

i.e. the connection gets established.

The next bug fix release of Python 2.7 will include OpenSSL 0.9.8x, which is the latest OpenSSL 0.9.8 bug fix. It still shows the error in connecting, so I wonder whether this is a bug that just doesn't get fixed for 0.9.8, or whether it's a bug in the server (that 1.0.1 somehow avoids).