We report that eight cadmium arenethiolate compounds with general formula n infinity[Cd(SAr)2] and cadmium phenylmethanethiolate n infinity[Cd(SBz)2] (Bz = CH2C6H5), when subjected to plasma desorption time-of-flight mass spectrometry, yield positive and negative ions up to 3.7 kDa. The spectra reveal extended series of ions containing both RS- and S2-. For the Cd(SAr)2 compounds (Ar = C6H5, C6H4-4-F, C6H4-4-Cl, C6H4-4-CH3, C6H4-4-OCH3, C6H4-4-C4H9, C6H4-2-CH3) there occur sequences of positive ions [Cdx(SAr)2x-1]+ (x = 1-8), [CdxS(SAr)2x-3]+ (x = 2-6), [CdxS2(SAr)2x-5]+ (x = 3-7), and [CdxS3(SAr)2x-7]+ (x = 4, 5, 7) and negative ions [CdxS(SAr)2x-1]-(x = 1-3), [CdxS2(SAr)2x-3]- (x = 2 - 4), and [CdxS3(SAr)2x-5]- (x = 3, 4) : not all ions are observed for all compounds, and other ions involving fragmentation of SAr are also present. A quite different array of ions occurs for Cd(SBz)2. In the positive ion spectrum, 21 of the 24 ions fall into three series : [CdSx-1(SBz)]+ (x = 2, 3); [CdxSx-2(SBz)3]+ (x = 2-8, 10-12); [CdxS-x3(SBz)5]+ (x = 3-11). The negative ions for Cd(SBz)2 also fit three series : [CdxSx(SBz)]- (x = 1-13); [CdxSx-1(SBz)3]- (x = 1, 2, 3); [CdSx-3(SBz)6]- (x = 3-5, 7-9). The occurrence of these series, the absence of preferred numbers of Cd atoms, and an absent preference for x = 4 ions from the solids known to contain linked Cd4 (adamantanoid) cages all indicate that the ions are formed not simply by excision from the solids. The ion distributions are interpreted in terms of processes which are probably associative during the initial formation of an energetic ion aggregate but are evidently dissociative from this intermediate. A staircase structural motif involving Cd2{SR}2 rhombuses sharing trans edges is proposed to account for the compositions and transformations of the series of ions.