Four europium compounds, LiEuAsS3 (I), KEuAsS3 (IIa), RbEuAsS3 (IIb), and CsEuAsS3 (IIc), containing As3+ were synthesized in molten alkali-metal polysulfide salts. An As-rich flux was found to be necessary to stabilize the pyramidal building unit [AsS3](3-). All crystallize in the monoclinic space group P2(1)/c with two new structure types. Compound I features a new coordination mode for the [AsS3](3-) unit and three-dimensional [Eu(AsS3)](-) framework. Compounds IIa-c are isostructural and feature a layer of [Eu(AsS3)](-) with an unusual mu(5)-sulfide anion in a umbrella-like geometry. The compounds are paramagnetic semiconductors with an energy gap of similar to 2.0 eV.