The phenylazo moiety and its donor‐ and acceptor‐substituted derivatives are studied as effective auxochromes to improve their sensitivity and resolution for distinguishing between the spiro (SP; OFF) and mero (ON) forms in molecular photoswitching applications. Thus, 13 azospiropyran derivatives were synthesized and their spectroscopic and photokinetic behaviors were studied. The quality of photochromic reactions of the synthesized photochromic compounds were compared using a dose–response model. Interestingly, by replacing the nitro group in 6‐nitrospiropyran (ε = 0.42 × 104 M−1 cm−1) with a simple phenylazo moiety, the SP form is still colorless and the color intensity of the merocyanine (MC) form is improved desirably by extending the conjugation length (1a, ε = 1.35 × 104 M−1 cm−1). The presence of a hydrophilic OH group or a CH3 group at the para position of phenylazo moiety revealed more or less the same photochromic properties as 1a. The OCH3 group substituted at position 6 of the phenylazo moiety at the para position of the azobenzene moiety effectively increased the photochromic properties with the maximum k‐value for SP to MC switching. Meanwhile, Cl, Br, COOH, and NO2 groups at the para position of the azobenzene moiety revealed the reduction in photochromic properties compared to 1a.