Memristive synapses based on conductive bridging RAMs (CBRAMs) utilize a switching layer having low binding energy with active metals for excellent analog conductance modulation, but the resulting unstable conductive filaments cause fluctuation and drift of the conductance. This tunability–stability dilemma makes it difficult to implement practical neuromorphic computing. A novel method is proposed to enhance the stability and controllability of conductive filaments by introducing imidazole groups that boost the nucleation of Cu nanoclusters in the ultrathin polymer switching layer through the initiated chemical vapor deposition (iCVD) process. It is confirmed that conductive filaments based on nanoclusters with specific gaps are generated in the copolymer medium using this method. Furthermore, by modulating the tunneling gaps, an ultra-wide conductance range of analog tunable conductive filaments is achieved from several hundreds of nS to a few mS with a sub-1 V driving voltage. Through this, both reliable and stable analog switching are achieved with low cycle-to-cycle and device-to-device weight update variations and separable state retention with 32 states. This approach paves the way for the extension of state availability in synaptic devices to overcome the tunability–stability dilemma, which is essential for the synaptic elements in neuromorphic systems.