The detection of intimacy plays a crucial role in the improvement of intimate relationship, which contributes to promote the family and social harmony. Previous studies have shown that different degrees of intimacy have significant differences in brain imaging. Recently, a few of work has emerged to recognise intimacy automatically by using machine learning technique. Moreover, considering the temporal dynamic characteristics of intimacy relationship on neural mechanism, how to model spatio-temporal dynamics for intimacy prediction effectively is still a challenge. In this paper, we propose a novel method to explore deep spatial-temporal representations for intimacy prediction by Attention-enhanced Cascade Convolutional Recurrent Neural Network (ACCRNN). Given the advantages of time-frequency resolution in complex neuronal activities analysis, this paper utilizes functional near-infrared spectroscopy (fNIRS) to analyse and infer to intimate relationship. We collect a fNIRS-based dataset for the analysis of intimate relationship. Forty-two-channel fNIRS signals are recorded from the 44 subjects' prefrontal cortex when they watched a total of 18 photos of lovers, friends and strangers for 30 seconds per photo. The experimental results show that our proposed method outperforms the others in terms of accuracy with the precision of 96.5%. To the best of our knowledge, this is the first time that such a hybrid deep architecture has been employed for fNIRS-based intimacy prediction.