In short, we report the synthesis and full characterization of a family of λ 5 -phosphinines dimers 2-6 based on the DCNP scaffold directly connected through a C-C bond or through various π-linkers. For the design, we relied on the Weitz type strategy where two ylidic P atoms are connected through a π-skeleton displaying an even number of sp 2 carbons. Based on a combined experimental and theoretical study, we show that while the absorption is moderately impacted by the nature of the linker, both the emission and the redox properties are strongly dependent on its nature. In particular, the two directly connected dimers 6a-b display two easily accessible and reversible oxidations, making them appealing multi-stage redox systems. Finally, the fluorescence of 6b was electrochemically modulated unambiguously showing that these λ 5 -phosphinines dimers behave as intrinsically switchable electroactive fluorophores. While DCNP derivatives are becoming an attractive class of photonic dyes, these first electrofluorochromism results illustrate the potential of this family for applications as luminescent switches or in typical functions of multi-stage redox systems (photocatalysis, 17 spintronics, 18 energy storage ).