Add a row at top:

import pandas as pd

employees = pd.DataFrame({
    'EmpCode': ['Emp002', 'Emp003', 'Emp004'],
    'Name': ['John', 'Doe', 'William'],
    'Occupation': ['Chemist', 'Statistician', 'Statistician'],
    'Date Of Join': ['2018-01-25', '2018-01-26', '2018-01-26'],
    'Age': [23, 24, 34]})

print("\n------------ BEFORE ----------------\n")
print(employees)

# New line
line = pd.DataFrame({'Name': 'Dean', 'Age': 45, 'EmpCode': 'Emp001',
                     'Date Of Join': '2018-02-26', 'Occupation': 'Chemist'
                     }, index=[0])

# Concatenate two dataframe
employees = pd.concat([line,employees.ix[:]]).reset_index(drop=True)

print("\n------------ AFTER ----------------\n")
print(employees)

C:\pandas>python example26.py
 
------------ BEFORE ----------------
 
   Age Date Of Join EmpCode     Name    Occupation
0   23   2018-01-25  Emp002     John       Chemist
1   24   2018-01-26  Emp003      Doe  Statistician
2   34   2018-01-26  Emp004  William  Statistician
 
------------ AFTER ----------------
 
   Age Date Of Join EmpCode     Name    Occupation
0   45   2018-02-26  Emp001     Dean       Chemist
1   23   2018-01-25  Emp002     John       Chemist
2   24   2018-01-26  Emp003      Doe  Statistician
3   34   2018-01-26  Emp004  William  Statistician
 
C:\pandas>