Pedipalpi Latreille, 1810 is a poorly studied clade of arachnids comprising the whip spiders (Amblypygi Thorell, 1883), short-tailed whip scorpions (Schizomida Petrunkevitch, 1945) and whip scorpions (Thelyphonida Cambridge, 1872). It has recently been shown that whip spiders coat their exoskeleton with a solid cement layer (cerotegument) that forms elaborate microstructures and turns the cuticle into a super-hydrophobic state. The amblypygid cerotegument provides taxonomic information due to its fine structural diversity, but its presence and variation in the sister groups was previously unknown. The present contribution reports the surface structure of the cuticle in species of Palpigradi, Thelyphonida, and Schizomida to determine if these taxa possess a solid epicuticular secretion coat. Scanning electron microscopy revealed that in addition to Amblypygi only species of Thelyphonida possess solid epicuticular secretion layers. Unlike in Amblypygi, in the Thelyphonida this layer does not usually form microstructures and is less rigidly attached to the underlying cuticle. A species of Typopeltis Pocock, 1894, which exhibited globular structures analogous to the amblypygid cerotegument, was an exception. Glandular structures associated with cement secretions in Amblypygi and Thelyphonida were considered homologous due to similar structure. Solid epicuticular secretion coats were absent from Schizomida, which is interpreted as a secondary loss despite the presence of slit-like glandular openings that appear to produce such epicuticular secretions. The micro-whip scorpion order Palpigradi Thorell, 1900 exhibited markedly different cuticular surface structures and lacked solid epicuticular secretions, consistent with the hypothesis that this order is not closely related to Pedipalpi.These results enhance the knowledge of the small, enigmatic orders of Arachnida.