I just setup my Yubikey 4 on Windows. How can I use master password for signing/encrypting when I don't have my key?
If the yubikey is not inserted I get an error "Please insert the card with serial number : XXXXXXXXXXX"
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The "master password" is not a replacement for your private key -- it is simply a security measure to prevent someone from reading your private key from disk (before being written to the disk, the private key is encrypted itself using your passphrase).
In other words, now that your key is on the Yubikey, you must always use the yubikey in order to sign or decrypt anything.