The introduction of poly(1H-pyrazolyl)borate anions, better known as scorpionates, as negatively charged ligands for a great diversity of metal cations has had a tremendous influence in coordination chemistry. The structures of two salts of tetrakispyrazolylborate, namely [tetrakis(3-phenyl-1H-pyrazol-1-yl)borato]thallium(I), [Tl(C₃₆H₂₈BN₈)], andcatena-poly[potassium-[μ₂-tetrakis(3-cyclopropyl-1H-pyrazol-1-yl)borato]], [K(C₂₄H₂₈BN₈)]_n, have been determined at 296 K in the monoclinicP2₁/candC2/cspace groups, respectively. In their crystal structures, the thallium salt presents discrete molecular motifs, while the potassium salt shows infinite polymeric chains. The¹³C and¹⁵N CPMAS (cross polarization magic angle spinning) NMR spectra of these compounds were recorded and the chemical shifts compared with theoretically calculated ones at the GIAO/B3LYP/6-311++G(d,p) level. Both techniques are complementary and mutually consistent.