The present study examined the psychological characteristics of the entrepreneurs and intrapreneurs in terms of six variables, namely, achievement orientation, innovativeness, internal locus of control, risk-taking propensity, proactiveness and self-efficacy, and such an examination was also done with reference to the following five demographic features: gender, education level, family background, work experience and age range of the entrepreneurs/intrapreneurs. The study was carried out with sample survey of 134 entrepreneurs (owner–managers) and 116 intrapreneurs (corporate managers) belonging to various service provider enterprises of India. All the psychological characteristics (except ‘risk-taking propensity’) were found as moderately positive in case of both male and female entrepreneurs and intrapreneurs without significant variation. The risk-taking propensity was perceived as ‘less positive’ by the entrepreneurs and it was found to be significantly higher for female intrapreneurs as compared to that of male intrapreneurs. The entrepreneurs belonging to business family background were found significantly better than the entrepreneurs belonging to rest of the backgrounds (namely, farming, service in private company and service in public/government organization) with regard to the characteristics like achievement orientation, innovativeness, internal locus of control and risk-taking propensity. In the matter of ‘risk-taking propensity’ of intrapreneurs, those from private sector service families were found to be better than intrapreneurs from farming and business families. In the matter of ‘self-efficacy’, intrapreneurs belonging to private service background were found to be better than intrapreneurs belonging to background of public/government service. Post-graduate entrepreneurs were found to be better in achievement orientation than others; non-graduate entrepreneurs were found more proactive than others; and non-graduates were found more innovative than post-graduates. Post-graduate intrapreneurs were found better in risk-taking propensity than graduates, as well as they were found better in achievement orientation than non-graduates; whereas self-efficacy of non-graduates was found better than that of graduates and non-graduates. Comparatively, younger entrepreneurs were found more proactive than others; and those in their middle ages were found to have high locus of control and risk-taking propensity than others. Middle-aged intrapreneurs were found comparatively better in internal locus of control than those who were relatively younger and relatively elder. All those who were elder (40 years and above) were found to be more proactive than those who were relatively younger. Those who were younger (for example, 25–30 years) were found to have less achievement orientation than rest of the intrapreneurs. There is no significant impact of work experience of the entrepreneurs and intrapreneurs found on their psychological characteristics (except on the proactiveness of the intrapreneurs). Age, gender and family background were found as important predictors in discriminating between the two groups of entrepreneurs—one with low level and other with moderate level of such characteristics. But, in case of intrapreneurs, the discriminant analysis has shown dissimilar results. The results of the study do not match fully with the findings of earlier research, and hence the research on personal characteristics of the entrepreneurs and intrapreneurs appeared to be inconclusive.