Halide perovskites, particularly zero-dimensional (0D) A 2 BX 6 -type structures, have garnered significant attention in diverse fields due to their exceptional photoelectric properties. This study focuses on the optical property regulation of 0D A 2 ZrCl 6 through nonprotonated cation substitution (A = [(CH 3 ) 3 SO] + and [(CH 3 ) 4 N] + ) combined with different guest ions (i.e., Sb 3+ , Bi 3+ , and Mn 2+ ). The varied host−guest interaction is regarded as the reason for the different luminescent behaviors. The Sb 3+ dopant has a weaker interaction with the host [ ( C H 3 ) 3 S O ] 2 Z r C l 6 t h a n M n 2 + d o e s . A s a r e s u l t , Sb 3+ @[(CH 3 ) 3 SO] 2 ZrCl 6 shows an excitation-dependent photoluminescence ranging from blue to orange, while Mn 2+ @[(CH 3 ) 3 SO] 2 ZrCl 6 exhibits only Mn 2+ dopant emission under different excitation wavelengths. Besides the dopant effect on the host−guest interaction, the organic cation can impact the host−guest behavior as well. [(CH 3 ) 3 SO] 2 ZrCl 6 and [(CH 3 ) 4 N] 2 ZrCl 6 have different preferences for dopant ions. Sb 3+ and Mn 2+ are favorable in the host [(CH 3 ) 3 SO] 2 ZrCl 6 , while Sb 3+ and Bi 3+ are adopted in [(CH 3 ) 4 N] 2 ZrCl 6 . Due to the varied emission colors from Sb 3+ and Bi 3+ dopants, [(CH 3 ) 4 N] 2 ZrCl 6 possesses diverse photoluminescence behaviors through dopant engineering. Inside [(CH 3 ) 4 N] 2 ZrCl 6 , Sb 3+ and Bi 3+ have a weak host−guest interaction, showing a varied PL from the host and guest emission centers under different excitations.