I am using Kentico 13, no workflow and the POST request works fine. The REST API call URL is like: https://domain.com/rest/cms.attachment/currentsite
and the request body XML is:
<CMS_Attachment>
<AttachmentName>NewAttachmentFile2.png</AttachmentName>
<AttachmentExtension>.jpg</AttachmentExtension>
<AttachmentSize>File Size in Bytes</AttachmentSize>
<AttachmentMimeType>image/x-jpg</AttachmentMimeType>
<AttachmentImageWidth>183</AttachmentImageWidth>
<AttachmentImageHeight>47</AttachmentImageHeight>
<AttachmentDocumentID>192</AttachmentDocumentID>
<AttachmentGroupGUID>Attachment Field GUID</AttachmentGroupGUID>
<AttachmentBinary>base64 encoded binarey data</AttachmentBinary>
</CMS_Attachment>
You need to change the AttachmentSize value to the actual file size in bytes, use appropriate AttachmentDocumentID, AttachmentGroupID - this is the attachments field GUID and also set the right base64 string for the binary data.
I just tested the above and works perfectly fine. I used this tool to get the base64 string