A new PCCP‐coordinated molybdenum platform comprising a coordinated alkyne was employed for the cleavage of molecular dinitrogen. The coordinated η2‐alkyne was left unaffected during this reduction. DFT calculations suggest that the reaction proceeds via an initially generated terminal N2‐complex, which is converted to a dinuclear μ‐(η1:η1)‐N2‐bridged intermediate prior to N−N bond cleavage. Protonation, alkylation and acylation of the resulting molybdenum nitrido complex led to the corresponding N‐functionalized imido complexes. Upon oxidation of the N‐acylated imido derivative in MeCN, a fumaronitrile fragment was built up via C−C coupling of MeCN to afford a dinuclear molybdenum complex. The key finding that the strong N≡N bond may be cleaved in the presence of a weaker, but spatially constrained C≡C bond contradicts the widespread paradigm that coordinated alkynes are in general more reactive than gaseous N2. A new molybdenum pincer for N2‐splitting and functionalization is reported. The N2‐cleavage affords a molybdenum nitrido complex and proceeds in the presence of a coordinated alkyne, that is, in the presence of a weaker C≡C bond. The spatially and rationally restricted alkyne moiety is also tolerated during N‐functionalization of the former nitrido complex.