Bicyclo[1.1.0]butanes (BCBs), a class of highly strained saturated bicyclic carbocycles, have garnered increasing attention in recent years. Functionalization of BCBs provides an efficient approach to access cyclobutane derivatives driven by a strain-releasing force. We report here a diastereoselective synthesis of multi-substituted cyclobutanes through the cycloaddition of BCBs with triazolinedione or nitrosoarenes. The subsequent cleavage of N–N or N–O bonds of cycloadducts provides cyclobutane derivatives containing cis-1,3-heteroatom substitutions.