1,7,8‐Polymetalated 3‐tert‐butyl‐8‐R‐4‐oxo‐4H‐pyrazolo[5,1‐c][1,2,4]triazines (M = Li, Na; R = CO2Et, CN, H, D, and Li) have been generated for the first time using acidic NH deprotonation and lithium/bromine exchange method at −112 ÷ −97°C. The rapid pyrazole ring opening degradation of the unstable 7‐lithio‐4‐oxopyrazolo[5,1‐c][1,2,4]triazines at −97°C led to formation of 2‐(6‐tert‐butyl‐5‐oxo‐4,5‐dihydro‐1,2,4‐triazin‐3(2H)‐ylidene)acetonitriles. Furthermore, lithium, sodium ((6‐tert‐butyl‐5‐oxo‐5H‐1,2,4‐triazin‐2,4‐diid‐3‐ylidene)(cyano)methyl)lithium was successfully generated from 7,8‐dibromo‐3‐tert‐butylpyrazolo[5,1‐c][1,2,4]triazin‐4(6H)‐one, sodium hydride, and tert‐butyl lithium, and an electrophile trapping using H2O, dimethylformamide, t‐BuCOCl, and PhCOCl allowed the selective side‐chain functionalization. Structures of the isolated products have been established on the basis of IR, 1H, 2H, 13C NMR, and high‐resolution mass spectra.