Hypocrellins, photoactive compounds isolated from fungus, were first employed as non-surfactant templates in the synthesis of ternary chalcogenide Cu3BiS3 and AgBiS2 crystallites via a facile ethanol-thermal process. It was also found that the used templates, poly (vinylpyrrolidone) (PVP), poly (ethylene glycol) (PEG), and hypocrellins had strong effect on the morphology of synthesized Cu3BiS3 and AgBiS2 and their catalytic polymerization products of an alkylsilane, C18H37SiH3 with water. In particular, the orthorhombic phase of wittichenite Cu3BiS3 with multi-armed microrods morphology and the cubic Schapbachite and hexagonal phase Matildite AgBiS2 with flower-like morphology were obtained when hypocrellins were used as templates at 180 degrees C for 20 h. Although, the used templates seem to have little effect on the crystalline grain size, compared with traditional PVP and PEG templates, hypocrellins have exhibited better directing actions. Furthermore, the polymerization products over Cu3BiS3 and AgBiS2 templated by hypocrellins showed good replica of the morphologies before polymerization while the polymerization products over Cu3BiS3 and AgBiS2 templated by PVP and/or PEG exhibited significant morphology change.