Early sexual initiation is linked to an increased risk of HIV/AIDS and other STIs among teenagers, as well as having multiple partners, not using contraception, unintended pregnancy, and illegal abortions. Aim. To identify the correlates and psychological effects of early sexual debut among not-in-union women in Ghana. A descriptive cross-sectional survey was used for this study using data from Ghana Multiple Indicator Cluster Survey (MICS) for the year 2017/2018. SPSS software was used for data analysis, bivariate analysis for association was done using chi-square, and the prediction was done using a binary logistic regression model. The national prevalence of nonmarital early sexual initiation this current study recorded was 56.9%. Predictors variables were age, 15-24/≥35 years (
AOR
=
1.51
, 1.28-1.78), ever educated (
AOR
=
0.50
, 0.43-0.60), urban address (
AOR
=
0.85
, 0.74-0.98), married/single (
AOR
=
1.23
, 1.07-1.42), cohabitation/single (
AOR
=
1.43
, 1.19-1.72), Greater Accra Region/Upper West Region (
AOR
=
0.67
, 0.49-0.92), and health insurance (
AOR
=
0.89
, 0.79-0.998). As the wealth indices of the woman decrease from the richest to poorest, the likelihood of early sexual debut inversely increases: fourth/richest (
AOR
=
1.23
, 1.04-1.45), middle/richest (
AOR
=
1.31
, 1.09-1.58), second/richest (
AOR
=
1.38
, 1.11-1.72), and poorest/richest (
AOR
=
1.44
, 1.12-1.86); use of the internet (
AOR
=
0.58
, 0.50-068); substance use and alcohol ever use (
AOR
=
1.32
, 1.17-1.49); cigarette ever use (
AOR
=
2.58
, 1.44-4.64); contraceptive use (
AOR
=
1.31
, 1.16-1.49); and ever heard of HIV (
AOR
=
59
, 0.42-0.82). In conclusion, the prevalence of early sexual debut is still high in Ghana, especially among the northern regions. Several factors predicted early sex debut, and low life satisfaction and happiness were related to early sexual debut.