A high degree of regioselectivity is observed in the photochemically induced cyclization of (E)‐2‐(2,3,6‐trichlorostyryl)benzothiazole (1a). According to the proposed mechanism, this compound was expected to afford two products, 3,4‐dichloro‐ and 1,4‐dichlorobenzothiazolo[3,2‐α]quinolinium chlorides (4a and 4a', respectively). However, this reaction produced 3,4‐dichlorobenzazolo[3,2‐α]quinolinium chloride (4a) as the sole product. On the other hand, irradiation of (E)‐2‐(2,3,5‐trichlorostyryl)benzothiazole (1b) failed to produce the expected 1,3‐dichlorobenzothiazolo[3,2‐α]quinolinium chloride (4b). Furthermore, (E)‐2,3‐difluorostrylbenzothiazole (1c) also failed to give the corresponding 1‐fluorobenzothiazolo[3,2‐α]quinolinium fluoride (4c). Interestingly, the irradiation of 2,6‐dichlorostyrylbenzothialole (1d) produced 4‐chlorobenzothiazolo[3,2‐α]quinolinium chloride (4d) in excellent yield. This paper presents the results of these investigations and a mechanistic rationale for the outcome of this reaction based on steric arguments and theoretical studies using a combination of molecular mechanics (MM+) and semiempirical quantum mechanical calculations (PM3/RHF/CI). Two‐dimensional high field nmr methods were employed to make complete assignments of the proton and carbon spectra of all new compounds.