1) If you use a standard PC USB Bluetooth adapter that requires separate software installation on your PC (e.g. Philips SHB6101):
Yes, you can listen to music from your PC and monitor calls via your phone simultaneously.
To do so, make sure to pair the phone with your Bluetooth headset first, then turn both the phone and headset off. Then pair or connect your headset with the PC and turn on your phone again.
However, you cannot have two voice or music connections simultaneously (e.g. stream music from PC and mobile phone simultaneously, or monitor voice both on the PC and the mobile phone at the same time).
2) If you use a USB Bluetooth Music/Voice adapter that does not require software installation (e.g. Philips SHB6111):
No, you cannot connect to your PC and phone simultaneously.