We report here on dialkyldithiocarbamates complexes of the type [C
6
H
3
(CH
3
)S
2
MS
2
CNR
2
] (M = As and Bi: R = CH
3
, C
2
H
5
, and CH
2
-CH
2
), prepared by the reaction of toluene-3,4-dithiolatoarsenic(III) and -bismuth(III) chlorides [C
6
H
3
(CH
3
)S
2
MCl] (M = As and Bi) with sodium/ammonium salts of dialkyldithiocarbamates [XS
2
CNR
2
] (X = Na and NH
4
: R = CH
3
, C
2
H
5
and CH
2
-CH
2
). The new derivatives were characterized by melting point, elemental analysis (C, H, N, S and As/Bi) and spectroscopic studies (IR,
1
H and
13
C NMR). Single crystal X-ray diffraction analyses of toluene-3.4-dithiolatoarsenic(III) dimethyldithiocarbamate and toluene-3,4-dithiolatoarsenic(III) pyrrolidine-dithiocarbamate revealed a monodentate chelating mode of the dimethyl as well as the pyrrolidine-dithiocarbamate moieties in these complexes.