A catalytic system‐controlled divergent reaction strategy was here reported to construct four types of intriguing spiroheterocyclic skeletons from simple and readily available starting materials via a precise chemical bond activation/n+1 annulation cascade. The tetraazaspiroheterocyclic and trizazspiroheterocyclic scaffolds could be independently constructed by a selective N−N bond activation/n+1 annulation cascade, a C(sp2)‐H activation/4+1 annulation and a novel tandem C(sp2)‐H/C(sp3)−H bond activation/4+1 annulation strategy, along with a broad scope of substrates, moderate to excellent yields and valuable transformations. More importantly, in these transformations, we are the first time to capture a N−N bond activation and a C(sp3)−H bond activation of pyrazolidinones under different catalytic system. Four types of novel and complicated spiropyrazolones from pyrazolidinones and diazopyrazolones were constructed via a precise chemical bond activation/n+1 annulation route, especially a selective N−N bond activation/n+1 annulation cascade and a novel tandem C(sp2)−H/C(sp3)−H bond activation/4+1 annulation strategy, and diazopyrazolones acted as unexpected 1C synthons.