We present a novel class of decision diagrams, called Biconditional Binary Decision Diagrams (BBDDs), that enable efficient logic synthesis for XOR-rich functions. BBDDs are binary decision diagrams where the Shannon’s expansion is replaced by the biconditional expansion. Since the biconditional expansion is based on the XOR/XNOR operations, XOR-rich logic circuits are efficiently represented and manipulated with canonical Reduced and Ordered BBDDs (ROBBDDs). Experimental results show that ROBBDDs have 37% fewer nodes on average compared to traditional ROBDDs. We exploit this opportunity in logic synthesis for XOR-rich functions. For this purpose, we developed a BBDD- based One-Pass Synthesis (OPS) methodology. The BBDD-based OPS is capable to harness the potential of novel XOR-efficient devices, such as ambipolar transistors. Experimental results show that our logic synthesis methodology reduces the number of ambipolar transistors by 49.7% on average with respect to state-of-art commercial logic synthesis tool. Considering CMOS technology, the BBBD-based OPS reduces the device count by 31.5% on average compared to commercial synthesis tool.