Attentional bias has been defined as the propensity of a person to allocate selective attention automatically to salient cues (Field and Powell, 2007). In the case of smoking, this bias implies that smokers are implicitly attracted by smoking-related stimuli, which produce behavioral, memory, and emotional effects (Volkow et al., 2006; Giardini et al., 2009). In more detail, scientific evidence pointed out that smoking is strongly supported by attentional bias that activates craving and urgency to smoke a cigarette. However, poor and conflicting data are available regarding the role of this cognitive bias on former smokers. The main aim of this study is to explore the occurrence of the attentional bias on of both current and former smokers, also with the aim to identify associations with behavioral, psychological and cognitive characteristic of participants. We collected data on 245 current, volunteers (male 50.6%; female 49.4%) aged 54.81 (SD = 14.352, range = 18–63), divided in current smokers (98), former smokers (102) and non-smokers (45). A combination of neuropsychology tests (Emotional Smoke Stroop Task and Go/no-Go task), and standardized questionnaires [Behavioral Inhibition System-Behavioral Approach System (BIS-BAS), Fagerström Test for Nicotine Dependence (FTND), Barratt Impulsiveness Scale, Motivational questionnaire] were used to assess the attentional bias, psychological variables, and smoking-related characteristics. Responses at the Emotional Smoke Stroop task revealed that current and former smokers are actually slower than non-smokers are when facing smoking cues, while performances at other Stroop conditions and at the Go/no-Go task are not statistically different. These results confirmed the occurrence of the attentional bias in current smokers, and above all points out that the same effect is present in former smokers. We found only small and selective correlations between attentional bias and psychological variables (e.g., impulsiveness and inhibition). In particular, impulsivity is not directly associated with the AB intensity. Also, smoking characteristics (e.g., years of smoking and dependence level) and the length of the period of abstinence do not seem to modulate implicit cognition of smoking cue. Our data support the idea that the attentional bias may be considered relevant in sustaining smoking and favoring relapse.