Passerini (P-3CR) and Passerini-Smiles reactions were investigated in azetidine-2,3-diones, affording the corresponding 3,3-disubstituted-β-lactams with complete diastereoselectivity in high yields. The study has been carried out using different isocyanides, carboxylic acids, and phenols showing the scope of both reactions. In addition, the regioselective synthesis of highly functionalized β-lactam-triazole hybrids has been developed via a Passerini/CuAAC sequence. Interestingly, the use of dialkynes/diazides or trialkynes/triazides as linkers in the CuAAC step has allowed the synthesis of C(2) and C(3) symmetric β-lactam-triazole hybrids, respectively.