解决方法
我发现通过VSTO Word对象设置签名更容易:
static void SetDefault(string signature) { Word.Application oWord = new Word.Application(); Word.EmailOptions oOptions; oOptions = oWord.Application.EmailOptions; oOptions.EmailSignature.NewMessageSignature = signature; oOptions.EmailSignature.ReplyMessageSignature = signature; //Release Word if (oOptions != null) System.Runtime.InteropServices.Marshal.ReleaseComObject(oOptions); if (oWord != null) System.Runtime.InteropServices.Marshal.ReleaseComObject(oWord); }