The frequency domain characteristics of acoustic emission can reflect issues such as rock structure and stress conditions that are difficult to analyze in time domain parameters. Studying the influence of immersion time on the mechanical properties and acoustic emission frequency domain characteristics of muddy mineral rocks is of great significance for comprehensively analyzing rock changes under water–rock coupling conditions. In this study, uniaxial compression tests and acoustic emission tests were conducted on sandstones containing montmorillonite under dry, saturated, and different immersion time conditions, with a focus on analyzing the effect of immersion time on the dominant frequency of rock acoustic emission. The results indicated that immersion time had varying degrees of influence on compressive strength, the distribution characteristics of dominant acoustic emission frequencies, the frequency range of dominant frequencies, and precursor information of instability failure for sandstones. After initial saturation, the strength of the rock sample decreased from 53.52 MPa in the dry state to 49.51 MPa, and it stabilized after 30 days of immersion. Both dry and initially saturated rock samples exhibited three dominant frequency bands. After different immersion days, a dominant frequency band appeared between 95 kHz and 110 kHz. After 5 days of immersion, the dominant frequency band near 0 kHz gradually disappeared. After 60 days of immersion, the dominant frequency band between 35 kHz and 40 kHz gradually disappeared, and with increasing immersion time, the dominant frequency of the acoustic emission signals increased. During the loading process of dry rock samples, the dominant frequency of acoustic emission signals was mainly concentrated between 0 kHz and 310 kHz, while after saturation, the dominant frequencies were all below 180 kHz. The most significant feature before the rupture of dry rock samples was the frequent occurrence of high frequencies and sudden changes in dominant frequencies. Before rupture, the characteristics of precursor events for initially saturated and immersed samples for 5, 10, and 30 days were the appearance and rapid increase in sudden changes in dominant frequencies, as well as an enlargement of the frequency range of dominant frequencies. After 60 days of immersion, the precursor characteristics of rock sample rupture gradually disappeared, and sudden changes in dominant frequencies frequently occurred at various stages of sample loading, making it difficult to accurately predict the rupture of specimens based on these sudden changes.