Based on collections made in the western Guiana Shield over the last 21 years, Characidium crandellii and C. declivirostre are redescribed and two similar species are described from Guyana. These species all have enlarged paired fins with three to four rays thickened ventrally on the pectoral fin and two rays thickened on the pelvic fin. The species can be separated from all other Characidium and Melanocharacidium by having the venter unscaled from the isthmus to the pelvic origin. Characidium crandellii is found in the Essequibo and Takutu River systems and in an isolated population above Tencua Falls in the Ventuari River and the upper Paragua River (Orinoco River basin). Characidium declivirostre is found throughout the right-bank, shield tributaries of the Orinoco River system and in the upper Negro River. Characidium duplicatum, new species, appears to be rare but widely distributed in the Essequibo River system. Characidium wangyapoik, new species, is only known from the upper Ireng River, Branco River basin, along the border between Brazil and Guyana.