Glans peeling is not necessarily syphilis. However, syphilis can also cause glans, but usually only after the chancre has formed and the glans appears edematous with a white fused surface.
If syphilis is suspected, a blood test can be done to look for syphilis seropositivity and agglutination tests to differentiate between syphilis and glans dehiscence caused by general infection with bacteria or other pathogens.