This Night Ride show was for 2 hours, the first hour presented by Peel and the second by Jon Curle. (The Radio Times listing for the show on BBC Genome describes it as "The world of words and music explored by John Peel and at 1.1 by Jon Curle. Produced by John F. Muir"). Looking at the PasB, it does not say which part of the show Peel finished and Curle started. Therefore I'm guessing that the Paddlin' Madelin' Home was the last song on Peel's section.
Peel's studio guest was Harvey Matusow and not Harry Matusow as listed on Ken Garner's The Peel Sessions book. Harvey Matusow was an American communist who became an FBI informer and was sent to jail for perjury before settling in England between 1965 and 1973. In England, he wrote a column for the underground paper Friends and produced experimental music, making an album for Head Records with the group he formed, Harvey Matusow's Jew's Harp Band. A controversial character, he later settled back in America, where he died in a car accident in 2001.
This show has most of the sessions at the beginning of the programme. Peggy Seeger was then the wife of Ewan MacColl. Both were associated with the more doctrinaire faction of the folk scene rather than the beatnik/hippy folk artists Peel favoured, so she is one of the more unlikely Night Ride session guests.