Conducive and fluorescent hollow micro/nanospheres have attracted great attention owing to their potential applications such as environmental clean-up, energy storage, sensors, and medical diagnosis. We report novel, tunable, and uniform hollow microspheres of conjugated poly(aniline-co-3-amino-9-ethyl-carbazole) (PAC) copolymer synthesized by a template-free method, namely a simple chemical oxidative copolymerization of aniline and 3-amino-9-ethyl-carbazole. The molecular structure of the copolymers has been systematically characterized by UV-vis, ATR-IR, Raman, and solid-state C-13 cross-polarization magic angle spinning NMR spectroscopies. The particle size and properties including dispersibility, thermostability, electrical conductivity, fluorescence emission and its sensitive quenching of PAC hollow microspheres can be significantly controlled by simply optimizing feed comonomer ratios and reaction parameters such as acidic media and oxidants used. The formation mechanism of PAC hollow microspheres and their sensitively and selectively sensing properties toward nitro-based explosives and Cu(II) ions with the limit of detection down to 5 mu M and 5 nM are demonstrated, respectively. In particular, the limit of detection for Cu2+ is superior as compared to literature reports.