I know we often examine names of witnesses to ancestors marriages but on the flip side, I am sure when trawling through parish registers on fiche or film or scans of original PR's online etc, we will have seen ancestors acting as witnesses to marriages of people in the parish, including ones who may or may not be relatives. It does help if you find an ancestor witnessing a marriage to someone of their surname. But you may be surprised to find an ancestor witnessing a marriage in the parish of a couple who you have not linked to your family, they may be family but they may have been friends or neighbours of the couple and they agreed to act as witnesses.
One example of an ancestor witnessing a marriage of a couple is my 4xgreat grandmother Sarah Bradford, previously Coombs, nee Unknown c1790-Feb 1851. She died just 5 weeks before the 1851 census and lived from at least 1812 in London. "Not born in county" in the 1841 census of Marylebone, Middlesex. Her first husband, my ancestor, died in 1831 and she had her banns read at St Marylebone church to James Bradford in July 1834, both widower and widow respectively, but I have never found a marriage yet they remained together and she took his surname. Sarah wed her first husband George Coombs circa 1810, I have a beady eye on the 1810 marriage in Axminster, Devon of Geo Coombs to Sarah Davy. But nothing concrete.
Sarah's eldest son Matthew George Coombs married at St James Paddington in July 1835, and Sarah and her 2nd husband James Bradford witnessed the wedding. Just under a month later on 10 August 1835 at St James Paddington, James and Sarah Bradford witnessed the marriage of William Smith, bachelor to Ann Jenkins, spinster. Having trawled through 1830-1840 marriages in Paddington Church these 2 1835 weddings are the only 2 instances where Sarah Bradford witnessed a wedding. I have had trouble trying to trace William Smith and Ann after their marriage due to the common name. They may have been family of the Coombs/Bradford's or just friends.
Goes to show how ancestors witnessing marriages can bring up leads, whether they turn out cold or not.