The invention provides a dual-mode imaging probe with pH response. The chemical structural formula of the dual-mode imaging probe is as shown in the formula (I). In the formula (I), X represents -C(CH3)2-, -O-, -S- or -Se-; Y represents F, Cl, Br or I; R1 and R2 are independently selected from H atom, C1-18 alkyl or -SO3R5; R5 represents C1-18 alkyl or benzyl; R3 and R4 are independently selected from C1-18 alkyl or benzyl. When a pH of the probe is 3.5-10.0, the fluorescence intensity ratio of emission light at 760nm and 670nm is gradually enhanced along with the reduction of the pH; the absorption intensity ratio at 760nm and 680nm is gradually enhanced along with the reduction of the pH; 760nm/680nm photo-acoustic signals are gradually enhanced along with the reduction of pH; the obvious pH-depended photo-acoustic signal variability is shown; pKa is 6.2. The dual-mode imaging probe is very applicable to detection of tumor pH I in both a fluorescence mode and a photo-acoustic mode. The invention also provides a preparation method and application of the probe.