Adducts of the ligand bis(1,2,4-triazol-1-yl)methane (tz(2)(CH2)) of the form AgX:tz(2)(CH2):ER3:MeCN (1:1:1:x) (X = NO3, R = Ph, E = P, As, or Sb, x = 1 or 2; X = NO2, ClO4, O3SCF3, E = P, R = Ph, x = 0, 1 or 2; X = NO3, ClO4, E = P, R = cy, x = 1; X = ClO4, E = As, R = Ph, x = 2) and AgNO3:tz(2)(CH2):P(o-tolyl)(3) (2:2:1) have been synthesized and characterized in the solid state and in solution by analyses, spectral (IR, far-IR, H-1 and C-13 NMR, ESI MS data) data, and conductivity measurements, In the one-dimensional polymers (characterized by X-ray studies) AgNO3:tz(2)(CH2):PPh3:CH3CN (1:1:1:1), AgClO4:tz(2)(CH2):PPh3:CH3CN (1:1:1:2), AgNO3:tz(2)(CH2):AsPh3:CH3CN (1:1:1:2), and AgNO3:tz(2)(CH2):SbPh3:CH3CN (1:1:1:2), the silver atom can be regarded as four-coordinate, the tz(2)(CH2) ligands behaving as bridging groups rather than chelates, with no pair of ligands being dominant, quasi-trans, in their interactions. The AgNO3:tz(2)(CH2):P(o-tolyl)(3) (2:2:1) adduct is a two-dimensional polymer containing two independent silver atoms, one four-coordinated unsymmetrically by a pair of triazolyl rings, one P(o-tolyl)(3), and a unidentate nitrate and the second by a quasi-symmetrical O2NO chelate and a pair of equivalent triazolyl rings.