Yes. Calls work on WebRTC, which means that it uses DTLS for encryption.
The signaling messages, which are responsible for exchanging DTLS fingerprints, are sent over the same channel that your regular messages are sent over. Calls are as MITM-secure as this channel is.
All you need to read about is how WebRTC works. Delta Chat isn’t doing anything special. https://webrtcforthecurious.com/ is a nice resource IMO.